JP7143294B2 - Photochromic polyrotaxane compound and curable composition comprising said photochromic polyrotaxane compound - Google Patents

Description

The present invention relates to a novel photochromic polyrotaxane compound and a curable composition comprising the photochromic polyrotaxane compound.

Photochromic compounds represented by naphthopyran compounds, fulgide compounds, spirooxazine compounds, etc., change color quickly when exposed to light containing ultraviolet rays such as sunlight or mercury lamp light, and when the light irradiation is stopped and placed in a dark place, It has a property of returning to the original color (photochromic property), and is used in various applications, especially as an optical material, taking advantage of this property.

For example, photochromic spectacle lenses that have been given photochromic properties through the use of photochromic compounds are rapidly colored and function as sunglasses outdoors where they are irradiated with light including ultraviolet rays such as sunlight. In indoor environments where there is no glasses, the color fades and the glasses function as normal transparent glasses, and the demand for them has been increasing in recent years.

In order to impart photochromic properties to optical materials, photochromic compounds are generally used in combination with plastic materials. Specifically, the following means are known.

(a) A method of directly forming an optical material such as a lens by dissolving a photochromic compound in a polymerizable monomer and polymerizing it. This method is called a kneading method.

(b) A method of providing a resin layer in which a photochromic compound is dispersed on the surface of a plastic molded article such as a lens by coating or cast polymerization. This method is called a lamination method.

(c) A method of joining two optical sheets with an adhesive layer formed of an adhesive resin in which a photochromic compound is dispersed. This method is called the binder method.

By the way, optical materials such as optical articles imparted with photochromic properties are further required to have the following characteristics.
(I) The degree of coloration (initial coloration) in the visible light region before irradiation with ultraviolet rays is low.
(II) The degree of coloring (coloring density) when irradiated with ultraviolet rays is high.
(III) The speed (discoloration speed) from the time when the irradiation of ultraviolet rays is stopped until the film returns to its original state is fast.
(IV) Good durability against repeated reversible action from coloring to fading.
(V) high storage stability;
(VI) It should be easy to mold into various shapes.
(VII) To impart photochromic properties without lowering mechanical strength.

Accordingly, various proposals have been made to satisfy the above requirements even when producing optical materials having photochromic properties by means of the above-mentioned (a), (b), and (c). .

The kneading method described above has the advantage that photochromic plastic lenses can be mass-produced at low cost using a glass mold. Currently, most photochromic plastic lenses are produced by this method (see Patent Documents 1 and 2). Since the conventional kneading method requires the lens substrate to have strength, it is necessary to increase the mechanical strength of the matrix resin in which the photochromic compound is dispersed. Therefore, it is difficult to express excellent photochromic properties. That is, since the degree of freedom of the molecules of the photochromic compound present in the matrix resin is lowered, the reversible photochromic reaction may be impaired.

Regarding such a kneading method, Patent Document 1 describes a method of adding a photochromic compound to a monomer composition containing an isocyanate monomer and a thiol monomer. Further, Patent Document 2 discloses a photochromic curable composition containing a specific (meth)acrylic polymerizable monomer and a photochromic compound.

However, although photochromic lenses molded by polymerizing and curing these compositions have high mechanical strength, there is still room for improvement in terms of photochromic properties, particularly fading speed.

On the other hand, in the lamination method and the binder method, the photochromic property is expressed in a thin layer formed on the surface of various substrates as compared with the kneading method described above (for example, Patent Document 3, Patent Document 4, Patent Document 5 reference). Therefore, the photochromic compound must be dissolved at a high concentration in order to develop a color density equivalent to that of the kneading method. In that case, depending on the type of photochromic compound, there are problems such as insufficient solubility and precipitation during storage. Moreover, since the layer exhibiting photochromic properties is thin, the durability of the photochromic compound may be inferior in some cases.

Patent Document 3 discloses that a photochromic curable composition is applied onto a plastic lens by spin coating or the like and photocured to form a photochromic coating layer (this lamination method is also called a coating method). . Further, in Patent Document 4, a member such as an elastomer gasket, an adhesive tape, or a spacer is used to secure a gap between a plastic lens and a glass mold, and a photochromic curable composition is poured into this gap and polymerized and cured. Therefore, a method for forming a photochromic layer (hereinafter also referred to as a two-step polymerization method) is disclosed. Furthermore, Patent Document 5 discloses the production of a laminated sheet in which a transparent carbonate sheet is bonded with a polyurethane resin adhesive layer containing a photochromic compound (binder method).

However, in any of Patent Documents 3 to 5, it was necessary to express photochromic properties by a thin layer containing a photochromic compound. Therefore, when a photochromic compound having low solubility is used, the color density tends to be low, and there is room for improvement in terms of the durability of the photochromic compound.

In addition, a photochromic curable composition containing a novel compound has been studied to address the above points of improvement (see Patent Document 6). Patent Document 6 discloses a photochromic curable composition containing a polyrotaxane compound. This polyrotaxane compound is a compound having a composite molecular structure consisting of an axial molecule and a plurality of cyclic molecules surrounding the axial molecule. Patent Document 6 discloses a cured product excellent in mechanical properties, moldability, color density, and color fading speed by blending a photochromic compound with the polyrotaxane compound.

International Publication No. 2012/176439 pamphlet WO 2009/075388 Pamphlet International Publication No. 2011/125956 pamphlet WO 2003/011967 Pamphlet International Publication No. 2013/099640 pamphlet International Publication No. 2015/068798 Pamphlet

In Patent Document 6, an excellent photochromic curable composition and a cured product are obtained by blending a polyrotaxane compound. However, in recent years, there has been a demand for developing even better photochromic properties in terms of color development density, color fading speed, and the like. Since there is basically a trade-off relationship between color development density and color fading speed, it is not easy to achieve both.

An object of the present invention is to provide a cured product capable of improving the fading speed while maintaining a high color density, a photochromic compound capable of obtaining the same, and a curable composition using the same. .

In order to solve the above problems, the inventors of the present invention conducted extensive studies, paid attention to polyrotaxane compounds, and conducted various studies. The reason why the photochromic curable composition using the polyrotaxane compound exhibits excellent photochromic properties can be inferred as follows. That is, since the cyclic molecule of the polyrotaxane can slide on the axial molecule, a space is formed around the cyclic molecule. It is believed that this space rapidly causes a reversible structural change in the photochromic compound, resulting in an improvement in the fading speed and an improvement in the color density. Furthermore, having a cyclic molecule into which a side chain has been introduced is thought to contribute to the rapid reversible structural change of the photochromic compound present in the vicinity of the highly flexible side chain.

However, the conventional method of obtaining a curable composition by mixing a polyrotaxane compound with another polymerizable compound and blending a photochromic compound therewith has room for improvement in the following points.

In other words, the probability that the photochromic compound exists in the vicinity of the polyrotaxane compound naturally decreases as the blending amount of the polyrotaxane compound decreases. This can be prevented by increasing the blending amount of the polyrotaxane compound, but since the viscosity of the polyrotaxane compound is generally extremely high, there arises a problem that it becomes difficult to handle in manufacturing the lens. As a result of studies conducted by the present inventors for the purpose of overcoming such problems, it was found that the photochromic property can be maximized by arranging the photochromic compound in the vicinity of the polyrotaxane compound at all times. was completed.

That is, according to the present invention,
(1) A polyrotaxane compound comprising an axial molecule and a plurality of cyclic molecules enclosing the axial molecule, wherein a side chain containing a photochromic site is bonded to at least one of the cyclic molecules, and the cyclic molecule comprises , a photochromic polyrotaxane compound (hereinafter sometimes simply referred to as component (A)) characterized by a cyclodextrin ring .

In the present invention, the above-described polyrotaxane has a plurality of cyclic molecules, in which the axial molecule penetrates through the rings of the cyclic molecules, and bulky groups are bonded to both ends of the axial molecule to prevent the cyclic molecule from coming off from the axial molecule due to steric hindrance. It is a molecular complex having a structure. Molecular complexes such as polyrotaxanes are generally called supramolecules.

The photochromic curable composition of the present invention can preferably adopt the following aspects.

(2) The photochromic polyrotaxane compound (component (A)) of (1) above, wherein a side chain containing a polymerizable group is further bonded to at least one of the cyclic molecules.

(3) The photochromic polyrotaxane compound (1) or (2), wherein the side chain containing the photochromic moiety has at least an ether bond.

(4) The photochromic polyrotaxane compound according to any one of (1) to (3), wherein the side chain containing the polymerizable group has at least an ether bond.

( 5 ) The above (1) to wherein the axial molecule consists of a chain main chain and bulky groups at both ends thereof, the chain main chain is formed of polyethylene glycol, and the bulky groups at both ends are adamantyl groups. ( 4 ) The photochromic polyrotaxane compound according to any one of (4).

( 6 ) The photochromic property according to any one of (1) to ( 5 ) above, wherein the photochromic moiety has at least one structure selected from the group consisting of naphthopyran, spirooxazine, spiropyran, fulgide, fulgimide, and diarylethene. Polyrotaxane compound.

( 7 ) The photochromic polyrotaxane compound according to any one of (1) to ( 6 ), wherein the photochromic moiety is indeno[2,1-f]naphtho[1,2-b]pyran.

( 8 ) the polymerizable group is an acrylic group, a methacrylic group, an allyl group, a vinyl group, a 4-vinylphenyl group, an epoxy group, an episulfide group, a thietanyl group, an OH group, an SH group, an _NH2 group, an NCO group, and The photochromic polyrotaxane compound according to any one of ( 2 ) to ( 7 ), which is at least one group selected from the group consisting of NCS groups.

( 9 ) The side chain containing the photochromic site is represented by the following formula (1)

where PC is a photochromic group,
R ¹ is a linear or branched alkylene group having 2 to 8 carbon atoms,
R ² is a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms having an acetyl group branch, or a carbon number having an ether bond is a linear or branched alkylene group of 3 to 8,
L is the following formula (2)

wherein R ³ is a direct bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms;
R ⁴ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or 1 to 20 carbon atoms. is a dialkylsilyl group having a linear or branched alkyl group, R ⁵ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms,
X ¹ and X ² are each independently a direct bond, O, or NH;
c is an integer of 0 to 50, d is an integer of 0 to 50, e is an integer of 0 or 1,
When c is 2 or more, the divalent groups of multiple units of c may be the same or different,
When d is 2 or more, the divalent groups of multiple units of d may be the same or different.
is a divalent group represented by
a is an integer from 1 to 50, b is an integer from 0 to 50,
When a is 2 or more, the divalent groups of the multiple units of a may be the same or different,
When b is 2 or more, the divalent groups of multiple units of b may be the same or different,
The photochromic polyrotaxane compound according to any one of (1) to ( 8 ) above.

( 10 ) The side chain containing the polymerizable group has the following formula (3)

wherein Z is a polymerizable group,
R ⁶ is a linear or branched alkylene group having 2 to 8 carbon atoms,
R ⁷ is a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms having an acetyl group branch, or a carbon number having an ether bond is a linear or branched alkylene group of 3 to 8,
L' is the following formula (2')

here,
R ³¹ is a direct bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms,
R ⁴¹ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or 1 to 20 carbon atoms. is a dialkylsilyl group having a linear or branched alkyl group of
R ⁵¹ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms;
X ¹¹ and X ²¹ are each independently a direct bond, O, or NH;
c ₁ is an integer of 0 to 50, d ₁ is an integer of 0 to 50, e ₁ is an integer of 0 or 1,
When c ₁ is 2 or more, the divalent groups of the multiple units of c ₁ may be the same or different,
When d ₁ is 2 or more, the divalent groups of multiple units of d ₁ may be the same or different.
is a divalent group represented by
f is an integer from 1 to 50, g is an integer from 0 to 50,
When f is 2 or more, the divalent groups of multiple units of f may be the same or different,
When g is 2 or more, the divalent groups of multiple units of g may be the same or different,
The photochromic polyrotaxane compound according to any one of (2) to ( 9 ) above.

( 11 ) 1 to 100% of the side chains bonded to the cyclodextrin ring are side chains containing the photochromic site, and 0 to 99% are side chains having the polymerizable group; The photochromic polyrotaxane compound according to any one of (1) to ( 9 ).

( 12 ) A curable composition comprising the photochromic polyrotaxane compound according to any one of (1) to ( 11 ) above and a polymerizable compound other than the photochromic polyrotaxane compound.

( 13 ) the polymerizable compound other than the photochromic polyrotaxane compound contains at least one radically polymerizable group selected from the group consisting of an acrylic group, a methacrylic group, an allyl group, a vinyl group, and a 4-vinylphenyl group; The curable composition according to ( 12 ) above, which is a compound having

( 14 ) The above ( 12 ), wherein the polymerizable compound other than the photochromic polyrotaxane compound is a compound having at least one polymerizable group selected from the group consisting of an epoxy group, an episulfide group, and a thietanyl group. curable composition.

( 15 ) The polymerizable compound other than the photochromic polyrotaxane compound has at least one polymerizable group selected from the group consisting of OH group, SH group, _NH2 group, NCO group, and NCS group. A curable composition according to ( 12 ) above.

( 16 ) A photochromic cured product obtained by curing the photochromic polyrotaxane compound according to any one of (2) to ( 11 ) above.

( 17 ) A photochromic cured product obtained by curing the curable composition according to any one of ( 12 ) to ( 15 ).

The photochromic polyrotaxane compound of the present invention exhibits excellent photochromic properties. Furthermore, even when a polymerizable compound other than the photochromic polyrotaxane compound is contained, it is possible to obtain a cured product exhibiting photochromic properties with excellent color density and color fading speed.

Schematic diagram showing the molecular structure of polyrotaxane. Schematic diagram showing the molecular structure of the photochromic polyrotaxane compound of the present invention.

The present invention
A polyrotaxane compound comprising an axial molecule and a plurality of cyclic molecules enclosing the axial molecule, wherein a side chain containing a photochromic site is bonded to at least one of the cyclic molecules to provide a photochromic polyrotaxane compound.

The present invention also provides a curable composition obtained by blending the photochromic polyrotaxane compound with a polymerizable compound other than the photochromic polyrotaxane compound. The details are described below.

(polyrotaxane skeleton)
Polyrotaxane is a known compound, and as shown in FIG. 1, the polyrotaxane molecule indicated as a whole by "1" is formed from a chain-shaped axial molecule "2" and a cyclic molecule "3". It has a complex molecular structure. That is, the chain-shaped axial molecule "2" is enclosed by a plurality of cyclic molecules "3", and the axial molecule "2" penetrates the inside of the ring possessed by the cyclic molecule "3". Therefore, ring molecule "3" can slide freely on axial molecule "2". Bulky terminal groups "4" are formed at both ends of the axial molecule "2" to prevent the cyclic molecule "3" from falling off from the axial molecule "2".

That is, as described above, since the cyclic molecule "3" can slide on the axial molecule "2", a space is secured that allows the reversible reaction of the photochromic compound, and high color density and fast color fading speed can be obtained. It is considered possible. Since the cyclic molecule is bound with a side chain having a photochromic site, the probability that the photochromic site is present in the space is increased, so it is thought that excellent photochromic properties can be exhibited.

In the photochromic polyrotaxane compound used in the present invention, various known ones can be employed as the axial molecule of the polyrotaxane. For example, the chain portion may be linear or branched as long as it can penetrate the ring of the cyclic molecule, and is generally formed of a polymer.

Examples of polymers that form the chain portion of such axial molecules include polyvinyl alcohol, polyvinylpyrrolidone, cellulose resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, and polypropylene glycol. , polyvinyl acetal, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, olefin resin (e.g. polyethylene, polypropylene, etc.), polyester, polyvinyl chloride, styrene resin (e.g. polystyrene, acrylonitrile-styrene copolymer resin, etc.) ), acrylic resin (e.g., poly(meth)acrylic acid, polymethyl methacrylate, polymethyl acrylate, acrylonitrile-methyl acrylate copolymer resin, etc.), polycarbonate, polyurethane, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral, polyisobutylene , polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (e.g. ABS resin), polyamide (e.g. nylon, etc.), polyimide, polydiene (e.g., polyisoprene, polybutadiene, etc.), polysiloxane (e.g., polydimethylsiloxane, etc.), polysulfone , polyimine, polyacetic anhydride, polyurea, polysulfide, polyphosphazene, polyketone polyphenylene, polyhaloolefin and the like. These polymers may be appropriately copolymerized or modified.

In the photochromic polyrotaxane compound used in the present invention, preferred polymers forming the chain portion include polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, Polypropylene, polyvinyl alcohol or polyvinyl methyl ether, most preferably polyethylene glycol.

Furthermore, the bulky group formed at both ends of the chain portion is not particularly limited as long as it is a group that prevents the cyclic molecule from detaching from the axial molecule. Mention may be made of fluoresceinyl groups, dinitrophenyl groups, and pyrenyl substrates. Of these, an adamantyl group is particularly preferred in terms of ease of introduction.

The molecular weight of the above-mentioned axial molecule is not particularly limited, but if it is too large, the compatibility with other components, such as other polymerizable compounds other than the photochromic polyrotaxane compound that is appropriately blended, tends to deteriorate. If it is too small, the mobility of the cyclic molecule tends to decrease and the photochromic properties tend to decrease. From such a point of view, the weight average molecular weight Mw of the axial molecule is, for example, preferably 1,000 to 100,000, more preferably 3,000 to 80,000, and preferably in the range of 5,000 to 30,000. It is particularly suitable.
However, in order to further improve the compatibility with other polymerizable compounds and suppress the increase in viscosity, the compound forming the axial molecule may be of low molecular weight. Specifically, the weight average molecular weight of the axial molecule is preferably 200 to 50,000, more preferably 1,000 to 20,000. In addition, this weight average molecular weight Mw is a value measured by the GPC measurement method described in the following examples.

Moreover, the cyclic molecule may have a ring having a size capable of enclosing the axial molecule as described above. Rings and dicyclohexanocrown rings may be mentioned. Among these, a cyclodextrin ring is particularly preferred.

The cyclodextrin ring includes α form (ring inner diameter 0.45 to 0.6 nm), β form (ring inner diameter 0.6 to 0.8 nm), and γ form (ring inner diameter 0.8 to 0.95 nm). In the present invention, α-cyclodextrin ring and β-cyclodextrin ring are particularly preferred, and α-cyclodextrin ring is most preferred.

A plurality of cyclic molecules having a ring as described above are clathrated in one axial molecule. The inclusion number of the molecule is preferably in the range of 0.001 to 0.6, more preferably 0.002 to 0.5, still more preferably 0.003 to 0.4. If the number of inclusions of the cyclic molecules is too large, the cyclic molecules are densely present with respect to one axial molecule, so that the mobility tends to decrease and the photochromic properties tend to decrease. On the other hand, if the number of clathrates is too small, the gaps between the axial molecules become narrow, and the gaps that allow the reversible reaction of the photochromic compound molecules are reduced, which also tends to lower the photochromic properties.

The maximum number of inclusions of cyclic molecules with respect to one axial molecule can be calculated from the length of the axial molecule and the thickness of the ring possessed by the cyclic molecule.

For example, in the case where the chain portion of the axial molecule is made of polyethylene glycol and the ring of the cyclic molecule is an α-cyclodextrin ring, the maximum inclusion number is calculated as follows.

That is, the length of _two repeating units [--CH.sub.2-- _CH.sub.2O-- ] of polyethylene glycol approximates the thickness of one α-cyclodextrin ring. Therefore, the number of repeating units is calculated from the molecular weight of this polyethylene glycol, and 1/2 of this number of repeating units is obtained as the maximum inclusion number of the cyclic molecule. Assuming that the maximum number of clathrates is 1.0, the number of clathrates of the cyclic molecule is adjusted within the range described above.

In the photochromic polyrotaxane compound used in the present invention, a side chain containing a photochromic site is introduced into the cyclic molecule described above. Further, a side chain containing a polymerizable group is introduced into the cyclic molecule described above. This side chain is indicated by "5" in FIG.
In the present invention, a photochromic site and a polymerizable group are introduced into this side chain. FIG. 2 shows an example of the photochromic polyrotaxane compound "1a" suitable for use in the present invention. Axle molecule "2", ring molecule "3", and bulky terminal group "4" are the same as described in FIG. Then, a photochromic site "6" and a polymerizable group (not shown) are introduced into the side chain "5" in FIG.
FIG. 2 shows the case where the photochromic site "6" is introduced into the first side chain "5a", which is one type of the side chain "5". As will be described in detail below, in the photochromic polyrotaxane compound "1a" of the present invention, in consideration of productivity and the like, the first side chain "5a" is introduced into the cyclic molecule "3", and the chain is further extended. , side chain "5". The photochromic moiety "6" can be introduced not only in the first side chain "5a" but also in the side chain "5". However, considering the productivity of the photochromic polyrotaxane compound of the present invention, it is preferable to introduce the photochromic moiety "6" into the first side chain "5a". Moreover, the polymerizable group can be introduced into both the first side chain "5a" and the side chain "5".

That is, by introducing such a side chain "5" (and/or the first side chain "5a") into the ring, it is possible to more reliably form an appropriate space between adjacent axial molecules, It is possible to reliably secure a gap that allows the reversible reaction of the photochromic compound molecule, and to develop excellent photochromic properties. Moreover, such side chain "5" forms a pseudo-crosslinked structure in the polyrotaxane, thereby improving the mechanical strength of the photochromic cured body formed using the photochromic polyrotaxane compound of the present invention. .

The side chains are not particularly limited, but the average molecular weight of such side chains is preferably 45 to 10,000, more preferably 100 to 8,000, and more preferably 200 to 10,000. It is more preferably 5,000, and particularly preferably 300 to 2,000.
The average molecular weight of this side chain can be adjusted by the amount of the compound used when introducing the side chain. Note that the average molecular weight of the side chain does not include the molecular weight of the photochromic portion or the polymerizable group.

If the side chain is too small, the function of securing a gap that allows the reversible reaction of the photochromic site will be insufficient, and if the side chain is too large, it will be difficult to arrange the photochromic site described later near the polyrotaxane. , it tends to be difficult to fully utilize the space secured by the polyrotaxane.

Furthermore, the side chain as described above is introduced by utilizing the functional group of the ring of the cyclic molecule and modifying this functional group. For example, the α-cyclodextrin ring has 18 hydroxyl groups as functional groups, through which side chains are introduced. That is, up to 18 side chains can be introduced into one α-cyclodextrin ring. In the present invention, 6% or more, particularly 30% or more of the total number of functional groups possessed by such rings are preferably modified with side chains in order to sufficiently exhibit the functions of the side chains described above. Incidentally, when side chains are bonded to 9 out of 18 hydroxyl groups of the α-cyclodextrin ring, the degree of modification is 50%. And, of course, the rest remain hydroxyl groups.

In the present invention, the side chain (organic chain) as described above may be linear or branched as long as the size is within the range described above. ring-opening polymerization; radical polymerization; cationic polymerization; anionic polymerization; can be introduced. Various known reactions can be used to extend the side chains at the ends of the side chains formed by this polymerization or the like, and photochromic sites and polymerizable groups described in detail below can be introduced. . However, a photochromic site or a polymerizable group may be directly bonded to the side chain. As described above, the side chain formed by polymerization or the like or the side chain extended using various reactions has an average molecular weight of 300 to 300 when the photochromic site and the polymerizable group are excluded, as described above. 2,000 is preferred.

For example, ring-opening polymerization can introduce side chains derived from cyclic compounds such as cyclic ethers, cyclic siloxanes, lactone compounds, cyclic acetals, cyclic amines, cyclic carbonates, cyclic iminoethers, and cyclic thiocarbonates. Among these, cyclic ethers, cyclic siloxanes, lactone compounds, and cyclic carbonates are preferably used from the viewpoints of easy availability, high reactivity, and easy adjustment of size (molecular weight). Specific examples of suitable cyclic compounds are as follows.
cyclic ethers;
ethylene oxide, 1,2-propylene oxide, epichlorohydrin, epibromohydrin, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, oxetane, 3-methyloxetane, 3,3-dimethyloxetane, Tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran.

cyclic siloxanes;
hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane.

lactone compounds;
4-membered ring lactones such as β-propiolactone, β-methylpropiolactone, L-serine-β-lactone and the like.
Five-membered ring lactones such as γ-butyrolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ-decanolactone, γ-dodecanolactone, α-hexyl-γ-butyrolactone, α-heptyl -γ-butyrolactone, α-hydroxy-γ-butyrolactone, γ-methyl-γ-decanolactone, α-methylene-γ-butyrolactone, α,α-dimethyl-γ-butyrolactone, D-erythronolactone, α-methyl-γ -butyrolactone, γ-nonanolactone, DL-pantolactone, γ-phenyl-γ-butyrolactone, γ-undecanolactone, γ-valerolactone, 2,2-pentamethylene-1,3-dioxolan-4-one, α- Bromo-γ-butyrolactone, γ-crotonolactone, α-methylene-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone and the like.
6-membered ring lactones such as δ-valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, δ-tridecanolactone, δ-tetradecanolactone, DL-mevalonolactone, 4-hydroxy-1-cyclohexanecarboxylic acid δ-lactone, monomethyl-δ-valerolactone, monoethyl-δ-valerolactone, monohexyl-δ-valerolactone, 1,4-dioxane -2-one, 1,5-dioxepan-2-one and the like.
7-membered ring lactones such as ε-caprolactone, monomethyl-ε-caprolactone, monoethyl-ε-caprolactone, monohexyl-ε-caprolactone, dimethyl-ε-caprolactone, di-n-propyl-ε-caprolactone, di-n-hexyl -ε-caprolactone, trimethyl-ε-caprolactone, triethyl-ε-caprolactone, tri-n-ε-caprolactone, ε-caprolactone, 5-nonyl-oxepan-2-one, 4,4,6-trimethyl-oxepan-2 -one, 4,6,6-trimethyl-oxepan-2-one, 5-hydroxymethyl-oxepan-2-one and the like.
8-membered ring lactones, such as ζ-enantholactone;
Other lactones such as lactone, lactide, dilactide, tetramethylglycoside, 1,5-dioxepan-2-one, t-butylcaprolactone and the like.

cyclic carbonates;
Ethylene carbonate, propylene carbonate, 1,2-butylene carbonate , glycerol 1,2-carbonate, 4-(methoxymethyl)-1,3-dioxolan-2-one, (chloromethyl)ethylene carbonate, vinylene carbonate, 4,5 -dimethyl-1,3-dioxol-2-one, 4-chloromethyl-5-methyl-1,3-dioxol-2-one, 4-vinyl-1,3-dioxolane-2-one, 4,5- Diphenyl-1,3-dioxolan-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one, 1,3-dioxan-2-one, 5-methyl-5-propyl- 1,3-dioxolan-2-one, 5,5-diethyl-1,3-dioxolan-2-one.

The above cyclic compounds may be used alone or in combination of two or more.

In the present invention, lactone compounds and cyclic carbonates are preferably used, among which ε-caprolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, γ-butyrolactone, etc. are particularly preferred, with ε-caprolactone being the most preferred.

In addition, when introducing a side chain by reacting a cyclic compound by ring-opening polymerization, the functional group (e.g., hydroxyl group) bonded to the cyclic compound has poor reactivity, and steric hindrance in particular prevents large molecules from directly reacting. can be difficult. In such a case, for example, in order to react caprolactone, etc., a low-molecular-weight compound such as propylene oxide is first reacted with a functional group to perform hydroxypropylation, thereby introducing a highly reactive functional group (hydroxyl group). After that, a means of introducing a side chain by ring-opening polymerization using the above-described cyclic compound can be adopted. Hereinafter, a side chain formed by ring-opening polymerization with a low-molecular-weight compound such as propylene oxide and a cyclic compound may be referred to as a first side chain (as described above, "5a" in FIG. ).

In the present invention, the polyrotaxane compound most preferably used is composed of a cyclic molecule having an α-cyclodextrin ring, with polyethylene glycol having adamantyl groups bonded to both ends as an axial molecule.

(A) Photochromic Polyrotaxane Compound; Photochromic Polyrotaxane Compound in which Side Chains Containing Photochromic Moieties are Bonded to Cyclic Molecules In the polyrotaxane compound used in the present invention, side chains containing photochromic moieties are bonded to cyclic molecules. As a result, the photochromic site can always be arranged in the vicinity of the polyrotaxane compound, so even when combined with a polymerizable compound other than the photochromic polyrotaxane compound, the fading speed can be increased while maintaining a high color density. It becomes possible.

The photochromic site can be bonded to the cyclic molecule by using the side chains described above and, if necessary, by further combining a linking group L. That is, the first side chain and a photochromic site having a linking group L are reacted to bond the first side chain and the linking group L, thereby introducing a chain including a photochromic site into the cyclic molecule. can be done. In this case, the "chain" includes the portion formed by the reaction between the "first side chain and the linking group L" and includes the portion of the first side chain and the linking group L. And, as described above, the "chain" corresponds to the side chain. However, as noted above, the photochromic moiety may be directly attached to the first side chain, in which case the first side chain can be considered the "chain", and the "chain" is the side chain (first The side chain becomes the side chain).
The average molecular weight of the "chain" excluding the photochromic portion is preferably 45 to 10,000, more preferably 100 to 8,000, even more preferably 200 to 5,000, and 300 ~2,000 is particularly preferred.

Known photochromic sites can be used, and these can be used alone or in combination of two or more.

Representative examples of such photochromic moieties include naphthopyran, spirooxazine, spiropyran, fulgide, fulgimide, and diarylethene.

Among them, indenonaphthopyran is preferable, and among them, indeno[2,1-f]naphtho[1,2-b]pyran because it can exhibit excellent photochromic properties particularly in terms of color development density and color fading speed. is particularly preferred.

Indeno[2,1-f]naphtho[1,2-b]pyran, which is exemplified as a particularly preferable photochromic moiety, has the following formula (4)

here,
R ⁸ and R ⁹ each independently represent a group directly linked to L described later, a hydroxyl group, an alkyl group, a haloalkyl group, an optionally substituted cycloalkyl group, an alkoxy group, an amino group (first, a group containing a secondary amine), a heterocyclic group having a ring-member nitrogen atom and bonded to the carbon atom to which it is bonded at the nitrogen atom (however, it may have a substituent), a cyano group , nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, halogen atom, optionally substituted aralkyl group, optionally substituted aralkoxy group, substituted an aryloxy group, an aryl group optionally having substituents, an alkylthio group, a cycloalkylthio group, an arylthio group optionally having substituents,
In addition, R ⁸ and R ⁹ are each independently two adjacent to each other together, an aliphatic ring which may contain an oxygen atom, a nitrogen atom, or a sulfur atom (however, it may have a substituent ) may form
R ¹⁰ and R ¹¹ each independently represent a group directly linked to L described later, a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, an alkyl carbonyl group, alkoxycarbonyl group, halogen atom, optionally substituted aralkyl group, optionally substituted aralkoxy group, optionally substituted aryloxy group or substituted is a good aryl group,
R ¹⁰ and R ¹¹ together are an aliphatic ring having 3 to 20 ring-member carbon atoms together with the carbon atom at position 13 to which they are bonded, an aromatic ring or A condensed polycyclic ring obtained by condensing an aromatic heterocyclic ring, a heterocyclic ring having 3 to 20 ring member atoms, or a condensed polycyclic ring obtained by condensing an aromatic ring or an aromatic heterocyclic ring to the above heterocyclic ring may be formed. well, provided that these rings may have substituents,
R ¹² and R ¹³ are each independently an optionally substituted aryl group or an optionally substituted heteroaryl group,
h is an integer from 0 to 4,
i is an integer from 0 to 4,
When h is 2 to 4, multiple R ⁸ may be the same or different,
When i is 2 to 4, multiple R ⁹ may be the same or different,
provided that at least one of the substituents on the aryl group or heteroaryl group of R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² or the substituent on the aryl group or heteroaryl group of R ¹³ is substituted as described later. It is represented by the group L.

In addition, in the above R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ , the substituents that these groups or the ring groups formed by these groups may have mainly control the color tone and the like. These substituents do not impair the effects of the present invention. Therefore, although not particularly limited, the groups exemplified for R ⁸ and R ⁹ are preferred.

In the above, the alkyl group preferably has 1 to 6 carbon atoms, the haloalkyl group preferably has 1 to 6 carbon atoms, the cycloalkyl group preferably has 3 to 8 carbon atoms, and the alkoxy group preferably has 1 to 6 carbon atoms, the alkylcarbonyl group preferably has 2 to 7 carbon atoms, the alkoxycarbonyl group preferably has 2 to 7 carbon atoms, and the aralkyl group preferably has 7 to 11 carbon atoms. The aralkoxy group preferably has 7 to 11 carbon atoms, the aryloxy group preferably has 6 to 12 carbon atoms, the aryl group preferably has 6 to 12 carbon atoms, and the alkylthio The groups preferably have 1 to 6 carbon atoms, cycloalkylthio groups preferably having 3 to 8 carbon atoms, and arylthio groups preferably having 6 to 12 carbon atoms.

Indeno[2,1-f]naphtho[1,2-b]pyrans that form photochromic sites are described in, for example, WO 1996/014596, WO 2001/019813, WO 2001/060811, WO Publication No. 2005/028465, WO2006/110221, International Publication No. 2007/073462, International Publication No. 2007/140071, International Publication No. 2008/054942, International Publication No. 2010/065393, International Publication No. 2011/10744 pamphlet, International Publication No. 2011/016582 pamphlet, International Publication No. 2011/025056 pamphlet, International Publication No. 2011/034202 pamphlet, International Publication No. 2011/078030 pamphlet, International Publication No. 2012/ No. 102409 pamphlet, International Publication No. 2012/102410 pamphlet, International Publication No. 2012/121414 pamphlet, etc. can be used without any limitation.

Next, the side chain containing the photochromic site is represented by the following formula (1)

here,
PC is a photochromic group,
R ¹ is a linear or branched alkylene group having 2 to 8 carbon atoms,
R ² is a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms having an acetyl group branch, or a carbon number having an ether bond is a linear or branched alkylene group of 3 to 8,
L is the following formula (2)

here,
R ³ is a direct bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms;
R ⁴ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or 1 to 20 carbon atoms. is a dialkylsilyl group having a linear or branched alkyl group of
R ⁵ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms;
X ¹ and X ² are each independently a direct bond, O, or NH;
c is an integer of 0 to 50, d is an integer of 0 to 50, e is an integer of 0 or 1,
When c is 2 or more, the divalent groups of multiple units of c may be the same or different,
When d is 2 or more, the divalent groups of multiple units of d may be the same or different.
is a divalent group represented by
a is an integer from 1 to 50, b is an integer from 0 to 50,
When a is 2 or more, the divalent groups of the multiple units of a may be the same or different,
When b is 2 or more, the divalent groups of multiple units of b may be the same or different. is.

Of these, particularly preferred groups are exemplified by
R ¹ is preferably an ethyl group, a propyl group, an isopropyl group, or a butyl group, particularly preferably an isopropyl group. 1 to 10 are preferable for a, and 1 is particularly preferable.

R ² is particularly preferably a butylene group, a pentylene group or a hexylene group. b is preferably 1 to 10, particularly preferably 2 to 8.

Further, in L represented by the formula (2),
R ³ is preferably a single bond (in which case X ¹ is directly bonded to the oxygen atom of the unit b), or an ethylene group, propylene group or cyclohexylene group. Furthermore, a single bond or an ethylene group is particularly preferred.

X ¹ and X ² are each a single bond (in which case the carbonyl group is directly bonded to R ³ and R ⁴ ) or O is more preferred.

^R4 is preferably an ethylene group, a propylene group, a butylene group or a dimethylsilyl group, particularly preferably an ethylene group or a dimethylsilyl group.

c is preferably 2, d is preferably 1 to 10, particularly preferably 1 to 5, and e is preferably 0.

Among these, particularly preferable examples of L are as follows.

As a matter of course, in the above formula (1), the portion excluding PC corresponds to the "chain", and the average molecular weight of the "chain" excluding PC is 45 to 10,000. It is preferably from 100 to 8,000, even more preferably from 200 to 5,000, and particularly preferably from 300 to 2,000.

(Photochromic polyrotaxane compound in which a chain containing a polymerizable group is further bonded to a cyclic molecule)
In the photochromic polyrotaxane compound of the present invention, a chain containing a polymerizable group may be further bonded to the cyclic molecule. As a result, a cured product having excellent photochromic properties can be obtained by polymerizing and curing the photochromic polyrotaxane compound alone or in combination with a polymerizable compound other than the photochromic polyrotaxane compound described below.

The chain containing such a polymerizable group utilizes the above-described side chain (first side chain) in the same manner as the chain containing the above-described photochromic site, and if necessary, by further combining a linking group L, It can bind to cyclic molecules. The terminal of the first side chain may be a polymerizable group, and in this case, the first side chain corresponds to a chain containing a polymerizable group. Further, when the first side chain and a polymerizable group-containing compound having a linking group L are reacted to bond the first side chain and the linking group L to introduce a polymerizable group into the cyclic molecule. In , the "chain" includes the portion formed by the reaction between the "first side chain and the linking group L", and includes the portion of the first side chain and the linking group L. And, as described above, the "chain" corresponds to the side chain. The average molecular weight of the "chain" excluding the polymerizable group is preferably 45 to 10,000, more preferably 100 to 8,000, even more preferably 200 to 5,000, 300 to 2,000 is particularly preferred.

That is, the chain containing a polymerizable group is represented by the following formula (3)

here,
Z is a polymerizable group,
R ⁶ is a linear or branched alkylene group having 2 to 8 carbon atoms,
R ⁷ is a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms having an acetyl group branch, or a carbon number having an ether bond is a linear or branched alkylene group of 3 to 8,

L' is the following formula (2')

here,
R ³¹ is a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms,
R ⁴¹ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or 1 to 20 carbon atoms. is a dialkylsilyl group having a linear or branched alkyl group of
R ⁵¹ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms;
X ¹¹ and X ²¹ are each independently a direct bond, O, or NH;
c ₁ is an integer of 0 to 50, d ₁ is an integer of 0 to 50, e ₁ is an integer of 0 or 1,
When c ₁ is 2 or more, the divalent groups of the multiple units of c ₁ may be the same or different,
When d ₁ is 2 or more, the divalent groups of multiple units of d ₁ may be the same or different.
is a divalent group represented by
f is an integer from 1 to 50, g is an integer from 0 to 50,
When f is 2 or more, the divalent groups of multiple units of f may be the same or different,
When g is 2 or more, divalent groups in a plurality of units of g may be the same or different.
is introduced into the cyclic molecule by

As a matter of course, in the above formula (3), the portion excluding Z corresponds to the "chain", and the average molecular weight of the "chain" excluding Z is 45 to 10,000. It is preferably from 100 to 8,000, even more preferably from 200 to 5,000, and particularly preferably from 300 to 2,000.

Typical examples of the polymerizable group include radically polymerizable groups such as acrylic, methacrylic, allyl, vinyl and 4-vinylphenyl groups. Depending on the type of compound, epoxy groups, episulfide groups, thietanyl groups, OH groups, SH groups, _NH2 groups, NCO groups, or NCS groups can also be used as they function as polymerizing groups.

Of these, particularly preferred groups are exemplified by
^R6 is preferably an ethyl group, a propyl group, an isopropyl group, or a butyl group, particularly preferably an isopropyl group. f is preferably 1 to 10, particularly preferably 1.

R ⁷ is particularly preferably a butylene group, a pentylene group or a hexylene group. g is preferably 1 to 10, particularly preferably 2 to 8.

In L' represented by the formula (2'),
R ³¹ is preferably a single bond, an ethylene group, a propylene group or a cyclohexylene group, and particularly preferably a single bond or an ethylene group.

X ¹¹ is preferably a single bond or O.

X ²¹ is preferably a single bond, O or NH.

R ⁴¹ is preferably an ethylene group, a propylene group, a butylene group or a dimethylsilyl group, particularly preferably an ethylene group or a dimethylsilyl group.

^R51 is preferably a methylene group, an ethylene group or a propylene group.

c ₁ is preferably 2, d ₁ is preferably 1 to 10, particularly preferably 1 to 5, and e ₁ is preferably 0.

Among these, the following are particularly preferred as L'.

Here, the epoxy group, episulfide group and thietanyl group react with the epoxy group, episulfide group, thietanyl group, _NH2 group and NCO group of the polymerizable compound other than the photochromic polyrotaxane compound of the present invention.

OH groups and SH groups react with NCO groups and NCS groups of polymerizable compounds other than the photochromic polyrotaxane compound of the present invention to form urethane bonds and thiourethane bonds.

The NCO group and NCS group react with the OH group, SH group, or NH ₂ group possessed by other polymerizable compounds other than the photochromic polyrotaxane compound of the present invention.

(Number of Side Chains Having Suitable Photochromic Sites and Side Chains Having Polymerizable Groups)
The number of side chains containing a photochromic site that can be introduced into one molecule of the polyrotaxane compound is not particularly limited, and can be 1 to 5000 per molecule. It is preferable to set the number to 3 to 1,000 because the color density is saturated and the photochromic portion cannot function effectively. This number of side chains is an average value.

The number of side chains containing a polymerizable group is also not particularly limited, and can be 0 to 5,000. Even if the polymerizable compound is blended, it may bleed out without bonding in the cured product, so the number is preferably 10 to 5,000. This chain number is an average value.

Further, when the cyclic molecule is a cyclodextrin ring, 1 to 100%, preferably 5 to 80%, more preferably 10 to 60% of the side chains bonded to the cyclodextrin ring have the photochromic site. A photochromic polyrotaxane compound having a chain and 0 to 99%, preferably 20 to 95%, more preferably 40 to 90% of which is a side chain having the polymerizable group, provides excellent photochromic properties. Especially preferred. However, as explained above, side chains (including the first side chain) are not introduced into all the functional groups of the cyclic molecule.
Moreover, the photochromic site and the polymerizable group may not be introduced into all of the side chains (including the first side chain). For example, when the polymerizable group of the polymerizable compound is a radically polymerizable group, the photochromic polyrotaxane compound combined with it is the cyclodextrin, considering productivity, photochromic properties, and polymerizability with other polymerizable compounds. Among the side chains bonded to the ring, 5 to 50% of the side chains having the photochromic site, 10 to 90% of the side chains having a radically polymerizable group, side chains having no photochromic site and polymerizable group (terminal is a hydroxyl group or other group) is more preferably 5 to 50%, the side chain having the photochromic site is 10 to 40%, and the side chain having the polymerizable group is 20 to 80%, and more preferably 10 to 40% of side chains having no photochromic sites and polymerizable groups.
The photochromic polyrotaxane compound of the present invention is not particularly limited, but preferably has a weight average molecular weight Mw of 6,000 to 200,000, more preferably 8,000 to 150,000. preferable. In particular, in order to improve the compatibility with other polymerizable compounds, introduce many photochromic moieties without excessively increasing the viscosity of the monomer before curing, and obtain excellent effects, the photochromic polyrotaxane compound is used. The weight average molecular weight Mw is more preferably 10,000 to 120,000, particularly preferably 7,000 to 100,000.

(Method for producing photochromic polyrotaxane compound)
Although the method for producing the photochromic polyrotaxane compound of the present invention is not limited, it can be produced by the following method.

First, a polyrotaxane skeleton is produced by a known method. Next, a first side chain is introduced into the cyclic molecule of the polyrotaxane skeleton by a known method. At this time, the terminal of the first side chain is preferably a reactive group (for example, an OH group, etc.).

Separately, it has a photochromic site, and at least a group capable of reacting with the first side chain is introduced into the photochromic site. Preferably, this group is the group forming said L.

Then, the photochromic polyrotaxane compound of the present invention can be produced by reacting the polyrotaxane having the first side chain with the group capable of forming L. The photochromic site and the first side chain may be directly reacted (in this case, L is a single bond).

The reaction between the group capable of forming L and the end of the first side chain is not particularly limited.

For example, when the terminal of the first side chain is an OH group, the L can be formed by performing an esterification reaction with a compound having a carboxylic acid terminal. Specifically, in the presence of a mineral acid such as sulfuric acid or hydrochloric acid, an organic acid such as an aromatic sulfonic acid, or a Lewis acid such as boron fluoride ether, the mixture is stirred in a solvent such as toluene while heating as necessary, The water produced can be azeotropically removed for the reaction. In the above-mentioned esterification reaction, water can be removed by using a drying agent such as anhydrous magnesium sulfate or molecular sieves, or by removing water in the presence of a dehydrating agent such as dicyclohexylcarbodiimide. can be removed.

Alternatively, L can also be formed by performing an esterification reaction with a compound whose terminal is a carboxylic acid halide. Specifically, in the presence of a base such as pyridine or dimethylaniline, in an ether solvent such as tetrahydrofuran, stirring is performed with heating as necessary, and the resulting hydrogen halide can be removed. .

Furthermore, L can also be formed by performing an esterification reaction with a compound having an acid anhydride terminal. Specifically, a method of stirring in a solvent such as toluene in the presence of a catalyst such as sodium acetate or pyridine while heating as necessary can be employed.

As another method, L can also be formed by performing a urethanization reaction with a compound having an NCO group at the end. Specifically, a method of stirring in the presence of an amine-based catalyst such as triethylenediamine or a tin-based catalyst such as dibutyltin dilaurate in the absence of a solvent or in a solvent such as toluene while heating as necessary can be employed.

As for the method of introducing a chain having a polymerizable group, the same method as described above can be employed. A compound in which the photochromic site is replaced with a polymerizable group may be reacted with the group capable of forming L'. Moreover, when the reactive group at the end of the first side chain is the polymerizable group in the present invention, it can be used as it is as the polymerizable group.

(Polymerizable compound other than photochromic polyrotaxane compound)
The photochromic composition of the present invention may optionally contain a polymerizable compound other than the photochromic polyrotaxane compound. Examples of such a polymerizable compound (which may be used as component (B)) include a radically polymerizable compound (B1), an epoxy-based polymerizable compound (B2), a urethane or urea compound capable of forming a urethane bond, a urea bond, or the like. Other polymerizable compounds (B4) other than the system polymerizable compound (B3) and (B1 to B3) can be mentioned. In particular, when a polymerizable group is introduced into the photochromic polyrotaxane compound, a polymerizable compound capable of reacting with such a polymerizable group is preferably used.

(B1) a radically polymerizable compound;
The radically polymerizable compound (B1) is preferably used particularly when a radically polymerizable functional group is introduced into the side chain of the photochromic polyrotaxane compound. (Meth) acrylic polymerizable compound (B1-1) having a vinyl group having a vinyl polymerizable compound (B1-2), allyl group having an allyl polymerizable compound (B1-3), silsesquioxane It is classified as a system polymerizable compound (B1-4).
Specific examples are shown below.

(B1) Examples of (meth)acrylic polymerizable compounds;
(B1-1-1) Bifunctional (meth)acrylic polymerizable compound The photochromic curable composition of the invention preferably contains (B1-1-1) a bifunctional (meth)acrylic polymerizable compound. Specific examples are shown below. Specifically, they are compounds represented by the following formulas (5), (6) and (7). The compound represented by the following formula (5) may be hereinafter simply referred to as (B1-1-1-1) component, and the compound represented by the following formula (6) may be hereinafter simply referred to as (B1-1-1 -2) may be used as a component, and the compound represented by the following formula (7) may be simply used as a (B1-1-1-3) component hereinafter. In addition, a bifunctional (meth) acrylic polymerizable compound having a urethane bond (hereinafter sometimes simply referred to as (B1-1-1-4) component), the (B1-1-1-1) component, the (B1-1-1-2) component, the (B1-1-1-3) component, and the (B1-1-1-4) bifunctional (meth) acrylic polymerizable compound that does not correspond to the component (hereinafter , may be simply referred to as the (B1-1-1-5) component).

(B1-1-1-1) a compound represented by the following formula (5)

In the formula, R ¹⁴ and R ¹⁵ are each a hydrogen atom or a methyl group, j and k are each independently an integer of 0 or more, and j+k is an average value of 2 or more and 50 or less.

The polymerizable compound represented by the above formula (5) is usually obtained in the form of a mixture of molecules with different molecular weights. Therefore, j and k are shown as average values.

Specific examples of the compound represented by the above formula (5) are as follows.
diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, Tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, dimethacrylate consisting of a mixture of polypropylene glycol and polyethylene glycol (having two repeating units of polyethylene and two polypropylene), polyethylene glycol diacrylate, Methacrylate (especially average molecular weight 330), polyethylene glycol dimethacrylate (especially average molecular weight 536), polyethylene glycol dimethacrylate (especially average molecular weight 736), tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate (especially average molecular weight 536), polyethylene glycol diacrylate (especially average molecular weight 258), polyethylene glycol diacrylate (especially average molecular weight 308), polyethylene glycol diacrylate (especially average molecular weight 508), polyethylene glycol diacrylate (especially average molecular weight 708), polyethylene glycol Methacrylate acrylates (especially average molecular weight 536).

(B1-1-1-2) a compound represented by the following formula (6)

wherein R ¹⁶ and R ¹⁷ are each a hydrogen atom or a methyl group;
R ¹⁸ and R ¹⁹ are each a hydrogen atom or a methyl group,
R ²⁰ is a hydrogen atom or a halogen atom,
B is -O-, -S-, -(SO ₂ )-, -CO-, -CH ₂ -, -CH=CH-, -C(CH ₃ )2-, -C(CH ₃ )(C ₆ H ₅ )-,
l and m are each an integer of 1 or more, and l+m is an average value of 2 or more and 30 or less.

The polymerizable compound represented by the above formula (6) is usually obtained in the form of a mixture of molecules with different molecular weights. Therefore, l and m are shown as average values.

Specific examples of the compound represented by formula (6) include the following bisphenol A di(meth)acrylates.

2,2-bis[4-methacryloyloxy/ethoxy)phenyl]propane (l+m=2), 2,2-bis[4-methacryloyloxy/diethoxy)phenyl]propane (l+m=4), 2,2-bis[ 4-methacryloyloxy/polyethoxy)phenyl]propane (l + m = 7), 2,2-bis(3,5-dibromo-4-methacryloyloxyethoxyphenyl)propane (l + m = 2), 2,2-bis(4- methacryloyloxydipropoxyphenyl)propane (l + m = 4), 2,2-bis[4-acryloyloxy-diethoxy)phenyl]propane (l + m = 4), 2,2-bis[4-acryloyloxy-polyethoxy)phenyl] Propane (l+m=3), 2,2-bis[4-acryloyloxy-polyethoxy)phenyl]propane (l+m=7), 2,2-bis[4- methacryloyloxy (polyethoxy)phenyl]propane (l+m=10 ), 2,2-bis[4- methacryloyloxy (polyethoxy)phenyl]propane (l+m=17), 2,2-bis[4- methacryloyloxy (polyethoxy)phenyl]propane (l+m=30), 2, 2-bis[4- acryloyloxy (polyethoxy)phenyl]propane (l+m=10), 2,2-bis[4- acryloyloxy (polyethoxy)phenyl]propane (l+m=20).

(B1-1-1-3) a compound represented by the following formula (7)

wherein R ²¹ and R ²² are each a hydrogen atom or a methyl group;
n is an average value of 1 to 20,
A and A' may be the same or different from each other, and each is a linear or branched alkylene group having 2 to 15 carbon atoms, and when there are multiple A's, the multiple A's are the same group or different groups.

The compound represented by the above formula (7) can be produced by reacting a polycarbonate diol with (meth)acrylic acid.

Examples of polycarbonate diols used here include the following. Specifically, polycarbonate diols (number average of 500 to 2,000 molecular weight);
Mixtures of two or more polyalkylene glycols, such as mixtures of trimethylene glycol and tetramethylene glycol, mixtures of tetramethylene glycol and hexamethylene diglycol, mixtures of pentamethylene glycol and hexamethylene glycol, tetramethylene glycol and octamethylene glycol a mixture of hexamethylene glycol and octamethylene glycol, etc.) polycarbonate diol (number average molecular weight 500 to 2,000) obtained by phosgenation;
Polycarbonate diols (number average molecular weight 500-2,000) obtained by phosgenation of 1-methyltrimethylene glycol;

(B1-1-1-4) Bifunctional (meth)acrylic polymerizable compound having urethane bond Component (B1-1-1-4) is typically a reaction product of polyol and polyisocyanate. Here, examples of polyisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate, Norbornene methane diisocyanate or methylcyclohexane diisocyanate may be mentioned.

On the other hand, examples of polyols include polyalkylene glycols having repeating units of ethylene oxide, propylene oxide and hexamethylene oxide having 2 to 4 carbon atoms, and polyester diols such as polycaprolactone diol. Also, polycarbonate diol, polybutadiene diol, or ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, Examples include 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and the like.

In addition, a reaction mixture obtained by further reacting a urethane prepolymer obtained by the reaction of these polyisocyanates and polyols with 2-hydroxy (meth) acrylate, and a reaction obtained by directly reacting the diisocyanate with 2-hydroxy (meth) acrylate A mixture such as urethane (meth)acrylate can also be used.

As the bifunctional (meth) acrylic polymerizable compound having a urethane bond, U-2PPA (molecular weight 482), UA-122P (molecular weight 1,100), U-122P (molecular weight 1, manufactured by Shin-Nakamura Chemical Co., Ltd.) , 100), U-108A, U-200PA, UA-511, U-412A, UA-4100, UA-4200, UA-4400, UA-2235PE, UA-160TM, UA-6100, UA-6200, U- 108, UA-4000, UA-512, EB4858 (molecular weight 454) manufactured by Daicel UCB, and UX-2201, UX3204, UX4101, 6101, 7101, 8101 manufactured by Nippon Kayaku Co., Ltd. .

(B1-1-1-5) Other bifunctional (meth)acrylic polymerizable compounds As the component (B1-1-1-5), both ends of the alkylene group which may have a substituent ( Examples include compounds having a meth)acryl group. Component (B1-1-1-5) preferably has an alkylene group with 6 to 20 carbon atoms. Specifically, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate and the like.

In addition, the (B1-1-1-5) component can include bifunctional (meth)acrylate monomers containing sulfur atoms. The sulfur atom preferably forms part of the molecular chain as a sulfide group. Specifically, bis (2-methacryloyloxyethylthioethyl) sulfide, bis (methacryloyloxyethyl) sulfide, bis (acryloyloxyethyl) sulfide, 1,2-bis (methacryloyloxyethylthio) ethane, 1,2- bis(acryloyloxyethyl)ethane, bis(2-methacryloyloxyethylthioethyl)sulfide, bis(2-acryloyloxyethylthioethyl)sulfide, 1,2-bis(methacryloyloxyethylthioethylthio)ethane, 1,2 -bis(acryloyloxyethylthioethylthio)ethane, 1,2-bis(methacryloyloxyisopropylthioisopropyl)sulfide and 1,2-bis(acryloyloxyisopropylthioisopropyl)sulfide.

The above (B1-1-1-1) component, (B1-1-1-2) component, (B1-1-1-3) component, (B1-1-1-4) component, and (B1- In 1-1-5) component, a single component can be used for each component, or a plurality of types described above can be used. When multiple types are used, the reference mass of the component (B1-1-1) is the total amount of the multiple types.

Next, (B1-1-2) the polyfunctional (meth)acrylic polymerizable compound will be described.

(B1-1-2) Polyfunctional (meth)acrylic polymerizable compound (B1-1-2) As the component, a compound represented by the following formula (8) (hereinafter simply (B1-1-2-1) component), a polyfunctional (meth) acrylic polymerizable compound having a urethane bond (hereinafter sometimes simply referred to as (B1-1-2-2) component), and the above (B1-1 -2-1) component, and a polyfunctional (meth)acrylic polymerizable compound that does not fall under the (B1-1-2-2) component (hereinafter simply referred to as (B1-1-2-3) component There is).

(B1-1-2-1) Compound Represented by Formula (8) Below Examples of polyfunctional (meth)acrylic polymerizable compounds include compounds represented by formula (8) below.

wherein R ²³ is a hydrogen atom or a methyl group,
R ²⁴ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,
R ²⁵ is a tri- to hexavalent organic group having 1 to 10 carbon atoms,
o is a number from 0 to 3 on average, and p is a number from 3 to 6.

The alkyl group having 1 to 2 carbon atoms represented by R ²⁴ is preferably a methyl group. Examples of the organic group represented by R ²⁵ include groups derived from polyols, trivalent to hexavalent hydrocarbon groups, and trivalent to hexavalent organic groups containing urethane bonds.

Specific examples of the compound represented by the above formula (8) are as follows. Trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene Glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate.

(B1-1-2-2) polyfunctional (meth)acrylic polymerizable compound having a urethane bond (B1-1-2-2) component is the polyisocyanate described in component (B1-1-1-4) It is obtained by reacting a compound with a polyol compound such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol, and is a compound having three or more (meth)acrylate groups in the molecule. As commercially available products, Shin-Nakamura Chemical Co., Ltd. U-4HA (molecular weight 596, functional group 4), U-6HA (molecular weight 1,019, functional group 6), U-6LPA (molecular weight 818, functional group 6) , U-15HA (molecular weight 2,300, functional group number 15).

(B1-1-2-3) Other polyfunctional (meth)acrylic polymerizable compounds The (B1-1-2-3) component is a compound obtained by modifying the end of a polyester compound with a (meth)acrylic group. . Various commercially available polyester (meth)acrylate compounds can be used depending on the molecular weight of the polyester compound used as the raw material and the modification amount of the (meth)acrylic group. Specifically, tetrafunctional polyester oligomer (molecular weight 2,500 to 3,500, Daicel UCB, EB80, etc.), hexafunctional polyester oligomer (molecular weight 6,000 to 8,000, Daicel UCB, EB450, etc.) , hexafunctional polyester oligomer (molecular weight 45,000 to 55,000, Daicel UCB Co., Ltd., EB1830, etc.), tetrafunctional polyester oligomer (particularly, molecular weight 10,000, Daiichi Kogyo Seiyaku Co., Ltd., GX8488B, etc.) and the like. .

Using the (B1-1-2) component ((B1-1-2-1) component, (B1-1-2-2) component, (B1-1-2-3) component) exemplified above As a result, the crosslink density is improved by polymerization, and the surface hardness of the obtained cured product can be increased. Therefore, it is preferable to include the component (B1-1-2) particularly in the case of forming a photochromic cured product (laminate) obtained by a coating method. Among the (B1-1-2) components, it is particularly preferable to use the (B1-1-2-1) component.

The above (B1-1-2-1) component, (B1-1-2-2) component, and (B1-1-2-3) component can be used as a single component in each component, A plurality of the types described above can also be used. When multiple types are used, the reference mass of the component (B1-1-2) is the total amount of the multiple types.

Next, the (B1-1-3) monofunctional (meth)acrylic polymerizable compound will be described.

(B1-1-3) Monofunctional (Meth)acrylic Polymerizable Compound Examples of the component (B1-1-3) include compounds represented by the following formula (9).

wherein R ²⁶ is a hydrogen atom or a methyl group,
^R27 is a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group;
q is an integer from 0 to 10;
r is an integer from 0 to 20;

Specific examples of the compound represented by the above formula (9) are as follows.

Methoxy polyethylene glycol methacrylate (especially average molecular weight 293), methoxy polyethylene glycol methacrylate (especially average molecular weight 468), methoxy polyethylene glycol acrylate (especially average molecular weight 218), methoxy polyethylene glycol acrylate (especially average molecular weight 454), stearyl methacrylate, lauryl methacrylate , methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, glycidyl methacrylate.

(B1-2) vinyl polymerizable compound;
Vinyl-based polymerizable compounds having a vinyl group include methyl vinyl ketone, ethyl vinyl ketone, ethyl vinyl ether, styrene, vinylcyclohexane, butadiene, 1,4-pentadiene, divinyl sulfide, divinyl sulfone, 1,2-divinylbenzene, 1 ,3-divinyl-1,1,3,3-tetramethylpropanedisiloxane, diethylene glycol divinyl ether, divinyl adipate, divinyl sebacate, ethylene glycol divinyl ether, divinyl sulfoxide, divinyl persulfide, dimethyldivinylsilane, 1,2 , 4-trivinylcyclohexane, methyltrivinylsilane, α-methylstyrene and α-methylstyrene dimer.

Among the vinyl-based polymerizable compounds exemplified above, α-methylstyrene and α-methylstyrene dimer function as polymerization modifiers and improve the moldability of the photochromic composition.

(B1-3) Allyl-Based Polymerizable Compound Examples of the allyl-based polymerizable compound having an allyl group include the following. Diethylene glycol bisallyl carbonate, methoxy polyethylene glycol allyl ether (especially average molecular weight 550), methoxy polyethylene glycol allyl ether (especially average molecular weight 350), methoxy polyethylene glycol allyl ether (especially average molecular weight 1500), polyethylene glycol allyl ether (especially average molecular weight 450) ), methoxy polyethylene glycol-polypropylene glycol allyl ether (especially average molecular weight 750), butoxy polyethylene glycol-polypropylene glycol allyl ether (especially average molecular weight 1600), methacryloyloxy polyethylene glycol-polypropylene glycol allyl ether (especially average molecular weight 560), phenoxy polyethylene glycol allyl ether (especially average molecular weight 600), methacryloyloxy polyethylene glycol allyl ether (especially average molecular weight 430), acryloyloxy polyethylene glycol allyl ether (especially average molecular weight 420), vinyloxy polyethylene glycol allyl ether (especially average molecular weight 560), Tyryloxy polyethylene glycol allyl ether (especially average molecular weight 650), methoxypolyethylene thioglycol allyl thioether (especially average molecular weight 730).

By acting as a chain transfer agent, the allyl-based polymerizable compound can improve the photochromic properties (color density, color fading speed) of the curable composition.

(B1-4) silsesquioxane polymerizable compound;
The silsesquioxane polymerizable compound has various molecular structures such as cage-like, ladder-like and random, and has a radically polymerizable group such as a (meth)acrylic group.

Examples of such silsesquioxane polymerizable compounds include those represented by the following formula (10).

In the formula, s is the degree of polymerization and is an integer from 3 to 100,
A plurality of R ²⁸ may be the same or different, and is a radically polymerizable group, an organic group containing a radically polymerizable group, a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a phenyl group, and at least one One ^R28 is a radically polymerizable group or an organic group containing a radically polymerizable group.

Here, the radically polymerizable group represented by R ²⁸ or the organic group containing a radically polymerizable group includes (meth)acrylic group; (meth)acryloyloxypropyl group; (3-(meth)acryloyloxypropyl)dimethyl Organic groups having (meth)acrylic groups such as siloxy groups; Allyl groups; Organic groups having allyl groups such as allylpropyl groups and allylpropyldimethylsiloxy groups; Vinyl groups; Vinyl groups such as vinylpropyl groups and vinyldimethylsiloxy groups and an organic group having

(B2) epoxy-based polymerizable compound;
This polymerizable compound has an epoxy group in the molecule as a polymerizable group. In particular, a hydroxyl group, an _NH2 group, and an NCO group are introduced as polymerizable functional groups into the side chains of the polyrotaxane (A). It is particularly suitable when

Such epoxy-based polymerizable compounds are roughly classified into aliphatic epoxy compounds, alicyclic epoxy compounds and aromatic epoxy compounds, and specific examples thereof include the following.
Aliphatic epoxy compounds such as ethylene oxide, 2-ethyloxirane, butyl glycidyl ether, phenyl glycidyl ether, 2,2′-methylenebisoxirane, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether , triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nona Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, diglycidyl ether of tris(2-hydroxyethyl) isocyanurate , and triglycidyl ethers of tris(2-hydroxyethyl)isocyanurate.

Alicyclic epoxy compounds include isophoronediol diglycidyl ether and bis-2,2-hydroxycyclohexylpropane diglycidyl ether.

Examples of aromatic epoxy compounds include resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, phenol novolac polyglycidyl ether, and cresol novolac polyglycidyl ether.

In addition to the above, an epoxy-based polymerizable compound having a sulfur atom in the molecule can also be used together with the epoxy group. Such sulfur-containing atom epoxy-based polymerizable compounds particularly contribute to improving the refractive index, and include linear aliphatic compounds and cycloaliphatic compounds, and specific examples thereof are as follows.

Examples of chain aliphatic sulfur-containing atom epoxy-based polymerizable compounds include bis(2,3-epoxypropyl) sulfide, bis(2,3-epoxypropyl) disulfide, bis(2,3-epoxypropylthio)methane, 1,2-bis(2,3-epoxypropylthio)ethane, 1,2-bis(2,3-epoxypropylthio)propane, 1,3-bis(2,3-epoxypropylthio)propane, 1, 3-bis(2,3-epoxypropylthio)-2-methylpropane, 1,4-bis(2,3-epoxypropylthio)butane, 1,4-bis(2,3-epoxypropylthio)-2 -methylbutane, 1,3-bis(2,3-epoxypropylthio)butane, 1,5-bis(2,3-epoxypropylthio)pentane, 1,5-bis(2,3-epoxypropylthio)- 2-methylpentane, 1,5-bis(2,3-epoxypropylthio)-3-thiapentane, 1,6-bis(2,3-epoxypropylthio)hexane, 1,6-bis(2,3- epoxypropylthio)-2-methylhexane, 3,8-bis(2,3-epoxypropylthio)-3,6-dithiaoctane, 1,2,3-tris(2,3-epoxypropylthio)propane, 2 , 2-bis(2,3-epoxypropylthio)-1,3-bis(2,3-epoxypropylthiomethyl)propane, 2,2-bis(2,3-epoxypropylthiomethyl)-1-( 2,3-epoxypropylthio)butane.

Cycloaliphatic sulfur-containing atom epoxy polymerizable compounds include 1,3-bis(2,3-epoxypropylthio)cyclohexane, 1,4-bis(2,3-epoxypropylthio)cyclohexane, 1,3 -bis(2,3-epoxypropylthiomethyl)cyclohexane, 1,4-bis(2,3-epoxypropylthiomethyl)cyclohexane, 2,5-bis(2,3-epoxypropylthiomethyl)-1,4 -dithiane, 2,5-bis[<2-(2,3-epoxypropylthio)ethyl>thiomethyl]-1,4-dithiane, 2,5-bis(2,3-epoxypropylthiomethyl)-2, 5-dimethyl-1,4-dithiane can be mentioned.

(B3) a urethane-based polymerizable compound (including a urea-based polymerizable compound);
In this polymerizable compound, repeating units of polymerization are linked by a urethane bond or a urea bond. It is effective when an OH group, SH group, _NH2 group, NCO group or NCS group is introduced.

For example, a urethane bond is formed by a reaction between a polyol and a polyisocyanate. Also included are thiourethane linkages.

A urea bond is formed by a reaction between a polyamine and a polyisocyanate, and the urea bond includes a thiourea bond formed by a reaction between a polyamine and a polyisothiacyanate.

As understood from the above description, in the present invention, the urethane- or urea-based polymerizable compound includes polyol (B3-1), polythiol (B3-2), polyamine (B3-3), polyisocyanate (B3- 4) A plurality of compounds are selected and used from polyisothiacyanate (B3-5) so that the above urethane bond (thiourethane bond) or urea bond (thiourea bond) is formed. .

Further, when a hydroxyl group, a mercapto group (SH group), an _NH2 group, an NCO group, or the like is introduced as a polymerizable group into the side chain of the polyrotaxane described above, such a urethane- or urea-based polymerizable compound (hereinafter , and may be collectively referred to as a "urethane-based polymerizable compound").

As a compound used as one type of such urethane-based polymerizable compounds, the following are specifically used.

(B3-1) polyol;
Polyol is a compound having two or more OH groups in one molecule, for example, di-, tri-, tetra-, penta-, hexa-hydroxy compounds, two or more OH groups in one molecule containing polyester (polyester polyol), polyether containing two or more OH groups in one molecule (hereinafter referred to as polyether polyol), polycarbonate containing two or more OH groups in one molecule (polycarbonate polyol) , polycaprolactone (polycaprolactone polyol) containing two or more OH groups in one molecule, and acrylic polymer (polyacrylic polyol) containing two or more OH groups in one molecule.

Specific examples of these compounds are as follows.

Aliphatic alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglucoside, pentaerythritol, di Pentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dolcitol, iditol, glycol, inositol, hexanetriol, triglycerol, diglyperol, triethylene glycol, polyethylene glycol, tris(2- hydroxyethyl)isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo[5,2,1,0,2,6]decane-di methanol, bicyclo[4,3,0]-nonanediol, dicyclohexanediol, tricyclo[5,3,1,1]dodecanediol, bicyclo[4,3,0]nonanedimethanol, tricyclo[5,3,1 , 1] dodecane-diethanol, hydroxypropyltricyclo[5,3,1,1]dodecanol, spiro[3,4]octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, cyclohexanetriol, multi Toll and lactitol.

Aromatic alcohols include dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl)pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, tetra Brombisphenol A may be mentioned.

Sulfur-containing polyols include bis-[4-(hydroxyethoxy)phenyl]sulfide, bis-[4-(2-hydroxypropoxy)phenyl]sulfide and bis-[4-(2,3-dihydroxypropoxy)phenyl]sulfide. , bis-[4-(4-hydroxycyclohexyloxy)phenyl]sulfide and bis-[2-methyl-4-(hydroxyethoxy)-6-butylphenyl]sulfide.

Compounds obtained by adding an average of 3 molecules or less of ethylene oxide and/or propylene oxide per hydroxyl group to the above sulfur-containing polyol include di-(2-hydroxyethyl) sulfide, bis(2-hydroxyethyl) disulfide, 1, 4-dithiane-2,5-diol, bis(2,3-dihydroxypropyl)sulfide, tetrakis(4-hydroxy-2-thiabutyl)methane, bis(4-hydroxyphenyl)sulfone, tetrabromobisphenol S, tetramethylbisphenol S, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 1,3-bis(2-hydroxyethylthioethyl)-cyclohexane.

Examples of polyester polyols include compounds obtained by a condensation reaction between polyols and polybasic acids.

Examples of polyether polyols include compounds obtained by reacting a compound having two or more active hydrogen-containing groups in the molecule with alkylene oxide, and modified products thereof.

Polycaprolactone polyols include compounds obtained by ring-opening polymerization of ε-caprolactone.

Polycarbonate polyols include compounds obtained by phosgenation of one or more low-molecular-weight polyols, and compounds obtained by transesterification using ethylene carbonate, diethyl carbonate, diphenyl carbonate, or the like.

Examples of polyacrylic polyols include compounds obtained by copolymerizing acrylic acid esters or methacrylic acid esters containing hydroxyl groups and monomers copolymerizable with these esters. (B3-2) Polythiol;
A polythiol is a compound having two or more SH groups in one molecule, and specific examples thereof include the following compounds.

Aliphatic polythiols include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, and 1,6-hexanedithiol. , 1,2,3-propanetrithiol, tetrakis(mercaptomethyl)methane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxy butane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo[2,2,1]hepta-exo-cis-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane , Thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto- 1-propanol (3-mercaptoacetate), diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl) ether, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), 1, 4-bis(3-mercaptobutyryloxy)butane, 1,4-butanediol bis(3-mercaptopropionate), 1,4-butanediol-bis(thioglycolate), 1,6-hexanediol- Bis(thioglycolate), tetraethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolethane tris(3 -mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-bis(2-mercaptoethyl thio)-3-mercaptopropane, dipentaerythritol hexakis(3-methyl lecaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris ( 3-mercaptobutyrate), 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, 2-mercaptomethyl-1,3-propanedithiol, 2-mercaptomethyl-1,4-butanedithiol , 2,4,5-tris(mercaptomethyl)-1,3-dithiolane, 2,2-bis(mercaptomethyl)-1,4-butanedithiol, 4,4-bis(mercaptomethyl)-3,5- Dithiaheptane-1,7-dithiol, 2,3-bis(mercaptomethyl)-1,4-butanedithiol, 2,6-bis(mercaptomethyl)-3,5-dithiaheptane-1,7-dithiol, 4-mercapto Methyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-bismercaptomethyl-1,4-dithiane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 5,7-dimercaptomethyl -1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,8-dimercaptomethyl-1 , 11-dimercapto-3,6,9-trithiaundecane and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

Aromatic polythiols include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl) Benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2- Bis(mercaptomethoxy)benzene, 1,3-bis(mercaptomethoxy)benzene, 1,4-bis(mercaptomethoxy)benzene, 1,2-bis(mercaptoethoxy)benzene, 1,3-bis(mercaptoethoxy)benzene , 1,4-bis(mercaptoethoxy)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris( mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4- tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 1,2,3-tris(mercaptomethoxy)benzene, 1,2,4-tris(mercaptomethoxy)benzene, 1,3, 5-tris(mercaptomethoxy)benzene, 1,2,3-tris(mercaptoethoxy)benzene, 1,2,4-tris(mercaptoethoxy)benzene, 1,3,5-tris(mercaptoethoxy)benzene, 1, 2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene, 1 , 2,3,5-tetrakis(mercaptomethyl)benzene, 1,2,4,5-tetrakis(mercaptomethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3, 5-tetrakis(mercaptoethyl)benzene, 1,2,4,5-tetrakis(mercaptoethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercapto methoxy)benzene, 1,2,4,5-tetrakis(mercaptomethoxy)benzene, 1,2,3,4-tetrakis(mercapto toethoxy)benzene, 1,2,3,5-tetrakis(mercaptoethoxy)benzene, 1,2,4,5-tetrakis(mercaptoethoxy)benzene, 2,2'-dimercaptobiphenyl, 4,4'-dimercapto biphenyl, 4,4'-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7 -naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol, 1,3-di(p-methoxyphenyl) Propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di(p-mercaptophenyl)pentane, 1,4-bis(mercapto propylthiomethyl)benzene.

Halogen-substituted aromatic polythiols include 2,5-dichlorobenzene-1,3-dithiol, 1,3-di(p-chlorophenyl)propane-2,2-dithiol, 3,4,5-tribromo-1,2 -dimercaptobenzene, 2,3,4,6-tetrachloro-1,5-bis(mercaptomethyl)benzene.

Examples of heterocyclic polythiols include 2-methylamino-4,6-dithiol-sym-triazine, 2-ethylamino-4,6-dithiol-sym-triazine, and 2-amino-4,6-dithiol-sym-triazine. , 2-morpholino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym-triazine, 2-methoxy-4,6-dithiol-sym-triazine, 2-phenoxy-4, 6-dithiol-sym-triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, 2-thiobutyloxy-4,6-dithiol-sym-triazine, 1,3,5-tris(3- mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione,
Aromatic polythiols containing sulfur atoms in addition to mercapto groups include 1,2-bis(mercaptomethylthio)benzene, 1,3-bis(mercaptomethylthio)benzene, and 1,4-bis(mercaptomethylthio)benzene. , 1,2-bis(mercaptoethylthio)benzene, 1,3-bis(mercaptoethylthio)benzene, 1,4-bis(mercaptoethylthio)benzene, 1,2,3-tris(mercaptomethylthio)benzene, 1,2,4-tris(mercaptomethylthio)benzene, 1,3,5-tris(mercaptomethylthio)benzene, 1,2,3-tris(mercaptoethylthio)benzene, 1,2,4-tris(mercaptoethyl thio)benzene, 1,3,5-tris(mercaptoethylthio)benzene, 1,2,3,4-tetrakis(mercaptomethylthio)benzene, 1,2,3,5-tetrakis(mercaptomethylthio)benzene, 1, 2,4,5-tetrakis(mercaptomethylthio)benzene, 1,2,3,4-tetrakis(mercaptoethylthio)benzene, 1,2,3,5-tetrakis(mercaptoethylthio)benzene, 1,2,4 , 5-tetrakis(mercaptoethylthio)benzene, and core alkylates of the above polythiols.

Aliphatic polythiols containing sulfur atoms in addition to mercapto groups include bis(mercaptomethyl)sulfide, bis(mercaptoethyl)sulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, bis(2- mercaptoethylthio)methane, bis(3-mercaptopropyl)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-(2-mercaptoethylthio)ethane, 1,2-(3-mercaptopropyl)ethane , 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2-bis(2-mercaptoethyl thio)-3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2, 3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)disulfide and bis(mercaptopropyl)disulfide.

Thioglycolic acid or mercaptopropionic acid esters of the above compounds include hydroxymethylsulfide bis(2-mercaptoacetate), hydroxymethylsulfide bis(3-mercaptopropionate), hydroxyethylsulfide bis(2-mercaptoacetate), Hydroxyethylsulfide bis (3-mercaptopropionate), Hydroxypropyl sulfide bis (2-mercaptoacetate), Hydroxypropyl sulfide bis (3-mercaptopropionate), Hydroxymethyl disulfide bis (2-mercaptoacetate), Hydroxymethyl Disulfide bis (3-mercaptopropionate), Hydroxyethyl disulfide bis (2-mercaptoacetate), Hydroxyethyl disulfide bis (3-mercaptopropionate), Hydroxypropyl disulfide bis (2-mercaptoacetate), Hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane-2,5-diol bis (2 -mercaptoacetate), 1,4-dithiane-2,5-diolbis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, 2,5-bis(2-mercapto ethyl)-1,4-dithiane, 2,5-bis(3-mercaptopropyl)-1,4-dithiane, 2-(2-mercaptoethyl)-5-mercaptomethyl-1,4-dithiane, 2-( 2-mercaptoethyl)-5-(3-mercaptopropyl)-1,4-dithiane, 2-mercaptomethyl-5-(3-mercaptopropyl)-1,4-dithiane, bis(2-mercaptoethyl thioglycolate) ester), bis thiodipropionate (2-mercaptoethyl ester), bis 4,4'-thiodibutyrate (2-mercaptoethyl ester), bis dithiodiglycolate (2-mercaptoethyl ester), bis dithiodipropionate (2-mercaptoethyl ester), 4,4′-dithiodibutyric acid bis(2-mercaptoethyl ester), thiodiglycolic acid bis(2,3-dimercaptopropyl ester), thiodipropionate bis(2,3 - dimercaptopropyl ester), bis dithiodiglycolate (2,3-dimercaptopropyl ester), dithiodipropionic acid (2,3-dimercaptopropyl ester).

Heterocyclic polythiols containing sulfur atoms other than mercapto groups include 3,4-thiophenedithiol, tetrahydrothiophene-2,5-dimercaptomethyl, and 2,5-dimercapto-1,3,4-thiadiazole. .

Examples of isocyanurate group-containing polythiols include 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate, 1,3,5 -tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanate A nurate is mentioned.

(B3-3) polyamine;
A polyamine is a compound having two or more _NH2 groups in one molecule, and specific examples thereof include the following compounds. Specifically, ethylenediamine, hexamethylenediamine, isophoronediamine, nonamethylenediamine, undecanemethylenediamine, dodecamethylenediamine, metaxylenediamine, 1,3-propanediamine, putrescine, 2-(2-aminoethylamino) ethanol, diethylenetriamine, p-phenylenediamine, m-phenylenediamine, melamine, 1,3,5-benzenetriamine.

(B3-4) polyisocyanate;
A polyisocyanate is a compound having two or more NCO groups in one molecule, and specific examples thereof include the following compounds.

Aliphatic isocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2′-dimethylpentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, deca methylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate 4-isocyanatomethyloctane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatomethyloctane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, 1,4-butylene Glycol dipropyl ether-ω,ω'-diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and 2-isocyanatopropyl-2,6-diisocyanatehexanoate. be done.

Alicyclic isocyanates include isophorone diisocyanate, norbornane diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2′-dimethyldicyclohexylmethane diisocyanate, bis(4- isocyanato n-butylidene) pentaerythritol, dimer acid diisocyanate, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-3-( 3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,1]- Heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2 -isocyanatoethyl)-bicyclo[2,2,1]-heptane, 2 -isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6- (2-isocyanatoethyl)-bicyclo[2,2,1]-heptane, 1,3,5-tris(isocyanatomethyl)cyclohexane.

Aromatic isocyanates include xylylene diisocyanate, bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene, α,α,α',α'-tetramethylxylylenediisocyanate, bis(isocyanatobutyl)benzene, bis( isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl)phthalate, mesitylylene triisocyanate, 2,6-di(isocyanatomethyl)furan, phenylene diisocyanate, tolylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate , dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methylnaphthalene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane -4,4'-diisocyanate, bibenzyl-4,4'-diisocyanate, bis(isocyanatophenyl)ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, triphenylmethane triisocyanate, polymeric MDI, naphthalene tri isocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, 4-methyl-diphenylmethane-3,5,2',4',6'-pentaisocyanate , phenyl isocyanate methyl isocyanate, phenyl isocyanate ethyl isocyanate, tetrahydronaphthylene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone Diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofurandi isocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate. be.

Sulfur-containing aliphatic isocyanates include thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethylsulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, dicyclohexylsulfide-4,4'-diisocyanate, 1- Isocyanatomethylthia-2,3-bis(2-isocyanatoethylthia)propane, 1,2-bis(2-isocyanatoethylthio)ethane, 1,1,2,2-tetrakis(isocyanatomethylthio)ethane , 2,2,5,5-tetrakis(isocyanatomethylthio)-1,4-dithiane, 2,4-dithiapentane-1,3-diisocyanate, 2,4,6-trithiaheptane-3,5- diisocyanate, 2,4,7,9-tetrathiapentane-5,6-diisocyanate, bis(isocyanatomethylthio)phenylmethane.

Aliphatic sulfide isocyanates include bis[2-(isocyanatomethylthio)ethyl]sulfide.

Examples of aromatic sulfide isocyanates include diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzylthioether, bis(4-isocyanate methylbenzene) sulfide and 4,4'-methoxybenzenethioethylene glycol-3,3'-diisocyanate.

Examples of aromatic disulfide isocyanates include diphenyl disulfide-4,4′-diisocyanate, 2,2′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3,3′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3,3′-dimethyldiphenyl disulfide-6,6′-diisocyanate, 4,4′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3,3′-dimethoxydiphenyl disulfide-4,4′-diisocyanate, 4, 4'-dimethoxydiphenyl disulfide-3,3'-diisocyanate.

Examples of aromatic sulfone-based isocyanates include diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzylidenesulfone-4,4'-diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate, 4- Methyldiphenylmethanesulfone-2,4'-diisocyanate, 4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzylsulfone, 4,4'-dimethyl Diphenylsulfone-3,3'-diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate, 4,4'-dimethoxybenzeneethylenedisulfone-3,3'-diisocyanate, 4,4 '-dichlorodiphenylsulfone-3,3'-diisocyanate.

Examples of sulfonic acid ester-based isocyanates include 4-methyl-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol ester and 4-methoxy-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol ester.

Examples of aromatic sulfonic acid amide isocyanates include 4-methyl-3-isocyanatobenzenesulfonylanilide-3'-methyl-4'-isocyanate, dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-dimethoxy benzenesulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3-isocyanate and benzenesulfonylanilide-4-methyl-3'-isocyanate.

Sulfur-containing heterocyclic isocyanates include thiophene-2,5-diisocyanate, thiophene-2,5-diisocyanatomethyl, 1,4-dithiane-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanatomethyl, 1,3-dithiolane-4,5-diisocyanate, 1,3-dithiolane-4,5-diisocyanatomethyl, 1,3-dithiolane-2-methyl-4,5-diisocyanatomethyl, 1,3-dithiolane-2, 2-diisocyanatoethyl, tetrahydrothiophene-2,5-diisocyanatotetrahydrothiophene-2,5-diisocyanatomethyl, tetrahydrothiophene-2,5-diisocyanatoethyl, tetrahydrothiophene-3,4-diisocyanatomethyl.

Furthermore, halogen-substituted, alkyl-substituted, alkoxy-substituted, and nitro-substituted polyisocyanates, prepolymer-type modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, biuret-modified products, dimerization or trimerization. Reaction products and the like can also be used.

(B3-5) polyisothiocyanate;
Polyisothiocyanate is a compound having two or more NCS groups in one molecule, and specific examples thereof include the following compounds.

Aliphatic isothiocyanates include 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, 1,6-diisothiocyanatohexane, p-phenylenediisopropylidenedi Isothiocyanates can be mentioned.

Alicyclic isothiocyanates include cyclohexyl isothiocyanate and cyclohexane diisothiocyanate.

Aromatic isothiocyanates include phenylisothiocyanate, 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5 -diisothiocyanate m-xylene diisocyanate, 4,4'-diisothiocyanate 1,1'-biphenyl, 1,1'-methylenebis(4-isothiocyanatobenzene), 1,1'-methylenebis(4-isothiocyanate 2 -methylbenzene), 1,1′-methylenebis(4-isothiocyanate 3-methylbenzene), 1,1′-(1,2-ethanediyl)bis(4-isothiocyanatobenzene), 4,4′-diiso Thiocyanatobenzophenone, 4,4'-diisothiocyanate 3,3'-dimethylbenzophenone, benzanilide-3,4'-diisothiocyanate, diphenyl ether-4,4'-diisothiocyanate, diphenylamine-4,4'-diiso Thiocyanate can be mentioned.

Heterocyclic isothiocyanates include 2,4,6-triisothiocyanate and 1,3,5-triazine.

Examples of carbonyl isothiocyanate include hexanedioyl diisothiocyanate, nonanedioil diisothiocyanate, carbonic diisothiocyanate, 1,3-benzenedicarbonyl diisothiocyanate, 1,4-benzenedicarbonyl diisothiocyanate, (2,2 '-bipyridine)-4,4'-dicarbonyldiisothiocyanate.

Furthermore, it is also possible to use polyfunctional isothiocyanates which have at least one sulfur atom in addition to the sulfur atoms of the isothiocyanate groups. Examples of such polyfunctional isothiocyanates include the following compounds.

Examples of sulfur-containing aliphatic isothiocyanates include thiobis(3-isothiocyanatopropane), thiobis(2-isothiocyanatoethane), and dithiobis(2-isothiocyanatoethane).

Sulfur-containing aromatic isothiocyanates include 1-isothiocyanate 4-{(2-isothiocyanate)sulfonyl}benzene, thiobis(4-isothiocyanatobenzene), sulfonylbis(4-isothiocyanatobenzene), sulfinylbis(4- isothiocyanatobenzene), dithiobis(4-isothiocyanatobenzene), 4-isothiocyanate 1-{(4-isothiocyanatophenyl)sulfonyl}-2-methoxy-benzene, 4-methyl-3-isothiocyanatobenzenesulfonyl-4' -isothiocyanate phenyl ester, 4-methyl-3-isothiocyanatobenzenesulfonylanilide-3'-methyl-4'-isothiocyanate.

The sulfur-containing heterocyclic isothiocyanate includes thiophene-2,5-diisothiocyanate and 1,4-dithiane-2,5-diisothiocyanate.

The urethane polymerizable compound (B3) described above is used in combination so as to form a urethane bond or a urea bond by polymerization.

(B4) other polymerizable compounds;
In the present invention, in addition to the polymerizable compounds (B1) to (B3) described above, an episulfide polymerizable compound (B4-1) and a thietanyl polymerizable compound (B4-2) are added for the purpose of improving the refractive index. A monofunctional polymerizable compound (B4-3) can also be used for the purpose of improving photochromic properties (however, the above-exemplified polymerizable compound having one polymerizable group is except.). Furthermore, a complex polymerizable compound (B4-4) having different types of polymerizable groups in the molecule (B4-4) can also be used.

(B4-1) Episulfide-based polymerizable compound;
This polymerizable monomer is a compound having two or more episulfide groups in the molecule, and in particular, an SH group is introduced as a polymerizable functional group into the side chain of the photochromic polyrotaxane compound (A). is suitable in some cases. Specifically, the following compounds can be exemplified. bis(1,2-epithioethyl)sulfide, bis(1,2-epithioethyl)disulfide, bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropylthio)methane, bis(2,3 -epithiopropyl)disulfide, bis(2,3-epithiopropyldithio)methane, bis(2,3-epithiopropyldithio)ethane, bis(6,7-epithio-3,4-dithiaheptyl)sulfide, bis (6,7-epithio-3,4-dithiaheptyl) disulfide, 1,4-dithiane-2,5-bis(2,3-epithiopropyldithiomethyl), 1,3-bis(2,3-epithio propyldithiomethyl)benzene, 1,6-bis(2,3-epithiopropyldithiomethyl)-2-(2,3-epithiopropyldithioethylthio)-4-thiahexane, 1,2,3-tris( 2,3-epithiopropyldithio)propane, 1,1,1,1-tetrakis(2,3-epithiopropyldithiomethyl)methane, 1,3-bis(2,3-epithiopropyldithio)-2 -thiapropane, 1,4-bis(2,3-epithiopropyldithio)-2,3-dithiabutane, 1,1,1-tris(2,3-epithiopropyldithio)methane, 1,1,1- tris(2,3-epithiopropyldithiomethylthio)methane, 1,1,2,2-tetrakis(2,3-epithiopropyldithio)ethane, 1,1,2,2-tetrakis(2,3-epi thiopropyldithiomethylthio)ethane, 1,1,3,3-tetrakis(2,3-epithiopropyldithio)propane, 1,1,3,3-tetrakis(2,3-epithiopropyldithiomethylthio)propane, 2-[1,1-bis(2,3-epithiopropyldithio)methyl]-1,3-dithietane, 2-[1,1-bis(2,3-epithiopropyldithiomethylthio)methyl]-1 , 3-dithiethane.

(B4-2) thietanyl-based polymerizable compound;
This polymerizable compound is effective when an SH group is introduced as a polymerizable functional group into the side chain of the photochromic polyrotaxane compound (A), and is a thietane compound having two or more thietanyl groups in the molecule. be. Some of such thietanyl-based polymerizable compounds have an episulfide group together with a plurality of thietanyl groups, which are listed in the above section on episulfide-based polymerizable compounds. Other thietanyl-based polymerizable compounds include metal-containing thietane compounds having a metal atom in the molecule and non-metallic thietane compounds containing no metal.

Examples of non-metallic thietane compounds include bis(3-thietanyl) disulfide, bis(3-thietanyl) sulfide, bis(3-thietanyl) trisulfide, bis(3-thietanyl) tetrasulfide, 1,4-bis(3- thietanyl)-1,3,4-trithibutane, 1,5-bis(3-thietanyl)-1,2,4,5-tetrathiapentane, 1,6-bis(3-thietanyl)-1,3,4 ,6,-tetrathiahexane, 1,6-bis(3-thietanyl)-1,3,5,6,-tetrathiahexane, 1,7-bis(3-thietanyl)-1,2,4,5 ,7-pentathiaheptane, 1,7-bis(3-thietanylthio)-1,2,4,6,7-pentathiaheptane, 1,1-bis(3-thietanylthio)methane, 1,2-bis( 3-thietanylthio)ethane, 1,2,3-tris(3-thietanylthio)propane, 1,8-bis(3-thietanylthio)-4-(3-thietanylthiomethyl)-3,6-dithiaoctane, 1, 11-bis(3-thietanylthio)-4,8-bis(3-thietanylthiomethyl)-3,6,9-trithiundecane, 1,11-bis(3-thietanylthio)-4,7-bis( 3-thietanylthiomethyl)-3,6,9-trithiundecane, 1,11-bis(3-thietanylthio)-5,7-bis(3-thietanylthiomethyl)-3,6,9-tri thiaundecane, 2,5-bis(3-thietanylthiomethyl)-1,4-dithiane, 2,5-bis[[2-(3-thietanylthio)ethyl]thiomethyl]-1,4-dithiane, 2, 5-bis(3-thietanylthiomethyl)-2,5-dimethyl-1,4-dithiane, bisthietanylsulfide, bis(thietanylthio)methane 3-[<(thietanylthio)methylthio>methylthio]thietane, bisthietanyl Disulfide, bisthietanyltrisulfide, bisthietanyltetrasulfide, bisthietanylpentasulfide, 1,4-bis(3-thietanyldithio)-2,3-dithibutane, 1,1,1-tris(3-thietanyldithio)methane , 1,1,1-tris(3-thietanyldithiomethylthio)methane, 1,1,2,2-tetrakis(3-thietanyldithio)ethane, 1,1,2,2-tetrakis(3-thietanyldithiomethylthio ) ethane.

As the metal-containing thietane compound, the thietane compound contains, in the molecule, as metal atoms, elements of Group 14 such as Sn atoms, Si atoms, Ge atoms, and Pb atoms; elements of Group 4 such as Zr atoms and Ti atoms; Group 13 elements such as Al atoms; or Group 12 elements such as Zn atoms;

Alkylthio(thietanylthio)tins include methylthiotris(thietanylthio)tin, ethylthiotris(thietanylthio)tin, propylthiotris(thietanylthio)tin, isopropylthiotris(thietanylthio)tin.

Bis(alkylthio)bis(thietanylthio)tin includes bis(methylthio)bis(thietanylthio)tin, bis(ethylthio)bis(thietanylthio)tin, bis(propylthio)bis(thietanylthio)tin, bis(isopropylthio)bis(thietanylthio)tin. ) tin.

Alkylthio(alkylthio)bis(thietanylthio)tin includes ethylthio(methylthio)bis(thietanylthio)tin, methylthio(propylthio)bis(thietanylthio)tin, isopropylthio(methylthio)bis(thietanylthio)tin, ethylthio(propylthio)bis(thietanylthio)tin. ) tin, ethylthio(isopropylthio)bis(thietanylthio)tin, isopropylthio(propylthio)bis(thietanylthio)tin.

The bis(thietanylthio)cyclic dithiotin compounds include bis(thietanylthio)dithiastanetan, bis(thietanylthio)dithiastanenolan, bis(thietanylthio)dithiastanninan, and bis(thietanylthio)trithiastanocan.

Alkyl(thietanylthio)tin compounds include methyltris(thietanylthio)tin, dimethylbis(thietanylthio)tin, butyltris(thietanylthio)tin, tetrakis(thietanylthio)tin.

Those containing metals other than tin include tetrakis(thietanylthio)germanium and tris(thietanylthio)bismuth.

(B4-3) a monofunctional polymerizable compound;
This polymerizable compound is a compound having one OH group or SH group in the molecule, is used in combination with the above-described polyol, and is used to enhance photochromic properties by adjusting the molecular weight and the degree of crosslinking. Examples of such monofunctional polymerizable compounds include the following compounds. polyethylene glycol monooleyl ether, polyethylene glycol monomethyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyethylene 2-ethylhexyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyethylene glycol mono-4-octylphenyl ether.

(B4-4) composite polymerizable compound;
This polymerizable compound has a plurality of different types of polymerizable groups in the molecule, and the use of such a polymerizable compound makes it possible to adjust various physical properties.

Examples of such complex polymerizable compounds include the following compounds.

Radical polymerization/OH type polymerizable compounds include 2-hydroxymethacrylate, 2-hydroxyacrylate, 2-hydroxypropyl acrylate, hydroxypropyl methacrylate and the like.

Radically polymerizable/isocyanate type polymerizable compounds include 2-isocyanatoethyl methacrylate and 2-isocyanatoethyl acrylate.

OH/SH type polymerizable compounds include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerin di(mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2 - mercaptohydroquinone, 4-mercaptophenol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris (3-mercaptopro pionate), pentaerythritol mono(3-mercaptopropionate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol tris(thioglycolate), pentaerythritol pentakis(3-mercaptopropionate), Hydroxymethyl-tris(mercaptoethylthiomethyl)methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4'-mercaptodiphenylsulfone, 2-(2-mercaptoethylthio)ethanol, dihydroxyethyl sulfide mono(3-mercaptopropionate), dimercaptoethane mono( salicylate ), hydroxyethylthiomethyltris(mercaptoethylthio)methane.

Among the polymerizable compounds (B1) to (B4) described above, the polymerizable compounds that are suitably used are the radical polymerizable compound (B1) and the urethane-based polymerizable compound (B3) in the kneading method, and the lamination method. is a radically polymerizable compound (B1) in the method, and a urethane-based polymerizable compound (B3) in the binder method.

(C) a polymerization curing accelerator;
In the photochromic composition of the present invention, depending on the type of the polymerizable functional group introduced into the side chain of the polymerizable compound (B) or the photochromic polyrotaxane compound (A), the polymerization and curing of the composition are rapidly accelerated. Various polymerization curing accelerators can be used for this purpose.

For example, when a radically polymerizable compound (B1) is used, and when a radically polymerizable functional group is introduced into the side chain of the photochromic polyrotaxane compound (A), the polymerization initiator (C1) is polymerized and cured. Used as an accelerator.

Further, when using a curable composition containing an epoxy-based polymerizable compound (B2), an episulfide-based polymerizable compound (B4-1), and a thietanyl-based polymerizable compound (B4-2), and a photochromic polyrotaxane compound ( When an epoxy group, an episulfide group, or a thietanyl group is introduced as a polymerizable functional group into the side chain of A), an epoxy curing agent (C2-1) and a cationic polymerization catalyst for ring-opening polymerization of the epoxy group (C2-2) is used as a polymerization curing accelerator.

Furthermore, when a urethane-based polymerizable compound (B3) or another polymerizable compound (B4) is used, and when the side chain of the photochromic polyrotaxane compound (A) has polymerizable functional groups such as OH, SH, and NH When _two groups, an NCO group, or an NCS group are introduced, a urethane reaction catalyst (C3-1) and a condensing agent (C3-2) are used as polymerization curing accelerators.

(C1) Polymerization Initiator Polymerization initiators include thermal polymerization initiators and photopolymerization initiators, and specific examples thereof are as follows.

Thermal polymerization initiators include diacyl peroxide such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide and acetyl peroxide.

Peroxyesters include t-butyl peroxy-2-ethylhexanate, t-butyl peroxyneodecanate, cumyl peroxyneodecanate, t-butyl peroxybenzoate.

Percarbonates include diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate.

Azo compounds include azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile).

Examples of photopolymerization initiators include acetophenone compounds such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 1-(4-isopropylphenyl)-2-hydroxy-2 -methylpropan-1-one.

Examples of α-dicarbonyl compounds include 1,2-diphenylethanedione and methylphenylglycoxylate.

Acylphosphine oxide compounds include 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphinic acid methyl ester, 2, 6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

In addition, when using a photopolymerization initiator, it is also possible to use a known polymerization curing accelerator such as a tertiary amine in combination.

(C2-1) Epoxy Curing Agent Amine compounds and salts thereof such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1,8-diaza-bicyclo(5,4,0)-7-undecene, trimethylamine, benzyldimethylamine, triethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 2-(dimethylaminomethyl)phenol.

Quaternary ammonium salts include tetramethylammonium chloride, benzyltrimethylammonium bromide, and tetrabutylammonium bromide.

Organic phosphine compounds include tetra-n-butylphosphonium benzotriazolate and tetra-n-butylphosphonium-0,0-diethylphosphorodithioate.

Metal carboxylates include chromium (III) tricarboxylate and tin octoate.

Acetylacetone chelate compounds include chromium acetylacetonate.

(C2-2) Cationic Polymerization Catalyst Examples of the Lewis acid catalyst include BF ₃ ·amine complex, PF ₅ , BF ₃ , AsF ₅ and SbF ₅ .

Examples of thermosetting cationic polymerization catalysts include phosphonium salts, quaternary ammonium salts, sulfonium salts, benzylammonium salts, benzylpyridinium salts, benzylsulfonium salts, hydrazinium salts, carboxylic acid esters, sulfonic acid esters and amine imides.

Examples of UV-curable cationic polymerization catalysts include diaryliodonium hexafluorophosphate and bis(dodecylphenyl)iodonium hexafluoroantimonate.

(C3-1) Reaction Catalyst for Urethane This reaction catalyst is used in the formation of poly(thio)urethane bonds by the reaction of polyiso(thia)cyanate with polyol or polythiol.

The following can be exemplified as this example. triethylenediamine, hexamethylenetetramine, N,N-dimethyloctylamine, N,N,N',N'-tetramethyl-1,6-diaminohexane, 4,4'-trimethylenebis(1-methylpiperidine), 1,8-diazabicyclo-(5,4,0)-7-undecene, dimethyltin dichloride, dimethyltin bis(isooctylthioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dibutyltin dichloride Sinolate, dibutyltin bis (dodecyl mercaptide), dibutyltin bis (isooctylthioglycolate), dioctyltin dichloride, dioctyltin maleate, dioctyltin maleate polymer, dioctyltin bis (butyl maleate), dioctyltin dilaurate, dioctyl Tin diricinolate, dioctyltin dioleate, dioctyltin di(6-hydroxy)caproate, dioctyltin bis(isooctylthioglycolate), didodecyltin diricinolate. Other examples include various metal salts such as copper oleate, copper acetylacetonate, iron acetylacetonate, iron naphthenate, iron lactate, iron citrate, iron gluconate, potassium octanoate, 2-ethylhexyl titanate and the like.

(C3-2) Condensing agent Examples of inorganic acids include hydrogen chloride, hydrogen bromide, sulfuric acid and phosphoric acid.

Examples of organic acids include p-toluenesulfonic acid and camphorsulfonic acid.

Examples of acidic ion exchange resins include styrene-divinylbenzene copolymers into which sulfonic acid groups are introduced.

Carbodiimides include dicyclohexylcarbodiimide and 1-ethyl-3-(3-dimethylaminopyrrolyl)-carbodiimide.

(Mixing ratio of polymerization curing accelerator (C))
The various polymerization curing accelerators (C) described above can be used either singly or in combination of two or more. A small amount in the range from 0.001 to 10 parts by weight, in particular from 0.01 to 5 parts by weight, per 100 parts by weight can be used.

Other ingredients in the curable composition;
The curable composition of the present invention contains various compounding agents known per se, such as release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, coloring agents, as long as they do not impair the effects of the present invention. Antistatic agents, antistatic agents, fluorescent dyes, dyes, pigments, various stabilizers such as perfumes, additives, solvents, leveling agents, and thiols such as t-dodecyl mercaptan as polymerization modifiers, if necessary can be compounded.

Among them, the use of an ultraviolet stabilizer is preferable because it can improve the durability of the photochromic portion. Hindered amine light stabilizers, hindered phenol antioxidants, sulfur-based antioxidants, and the like are known as such ultraviolet stabilizers. Particularly suitable UV stabilizers are as follows. Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, manufactured by Asahi Denka Kogyo Co., Ltd. Adekastab LA-52, LA-57, LA-62, LA-63, LA-67, LA- 77, LA-82, LA-87, 2,6-di-tert-butyl-4-methyl-phenol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl ) Propionate], IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565 manufactured by Ciba Specialty Chemicals.

The amount of the UV stabilizer used is not particularly limited as long as it does not impair the effects of the present invention, but it is usually 0.001 to 10 parts by weight, particularly 0.001 to 10 parts by weight, per 100 parts by weight of the photochromic polyrotaxane compound. 01 to 1 part by mass. In particular, when using a hindered amine light stabilizer, as a result of the difference in the effect of improving durability depending on the type of photochromic site, in order to prevent color shift in the adjusted color tone, 0.5 per 1 mol of photochromic site. The amount is preferably from 1 to 30 mol, more preferably from 1 to 20 mol, and still more preferably from 2 to 15 mol.

Photochromic compounds other than the photochromic polyrotaxane compound (A) can also be blended as long as the effects of the present invention are not impaired.

<Preferred Composition of Curable Composition>
The photochromic polyrotaxane compound of the present invention, especially when it has a polymerizable group, can be polymerized alone to obtain a photochromic cured product.

Also, the photochromic polyrotaxane compound (A) can be used in combination with the polymerizable compound (B).

In any case, in order to obtain a sufficient color density, the mass corresponding to the photochromic site should be 0.001 to 10% by mass when the total amount of the curable composition is 100% by mass. is preferred.

The mass corresponding to the photochromic portion varies depending on the method of expressing the photochromic property. When the photochromic property is expressed by the lamination method and the binder method, the content is preferably 0.1 to 10% by mass, particularly preferably 1 to 7% by mass.

Furthermore, the compounding ratio of the photochromic polyrotaxane compound (A) and the polymerizable compound (B) varies depending on how many side chains having photochromic moieties are included in one molecule of the photochromic polyrotaxane.

When the number of side chains of the photochromic site contained in one molecule is 1 to 30, the photochromic polyrotaxane compound (A) is 0.5 to 80% by mass, and the polymerizable compound (B) is 20 to 99.5% by mass. % by weight, and when the number of side chains of the photochromic site contained in one molecule is 30 to 300, the photochromic polyrotaxane compound (A) is added in an amount of 0.1 to 50% by weight, It is preferable to blend the polymerizable compound (B) in a proportion of 50 to 99.9% by mass. ) in an amount of 0.01 to 20% by mass and the polymerizable compound (B) in an amount of 80 to 99.99% by mass.

Furthermore, in the present invention, in order to maximize the photochromic improvement effect of the photochromic polyrotaxane compound (A), the type of the photochromic polyrotaxane compound (A) and the type of the polymerizable compound (B) to be used It can be determined accordingly.

When the polymerizable functional group to be introduced into the side chain of the photochromic polyrotaxane compound (A) is an acrylic group and/or a methacrylic group, the polymerizable compound (B) is used in combination with the radically polymerizable compound (B1). It is best to

At that time, the mixing ratio of component (B1) is when the total amount of component (B1-1), component (B1-2), component (B1-3), and component (B1-4) is 100% by mass. , Considering the hardness, mechanical properties, and photochromic properties such as color density and fading speed of the resulting photochromic cured product, the component (B1-1) is 80 to 100% by mass, (B1-2), (B1- 3) and (B1-4) are preferably combined in an amount of 0 to 20% by mass. Further, when the total amount of component (B1-1) is 100% by mass, component (B1-1-1) is 30 to 80% by mass, component (B1-1-2) is 10 to 50% by mass, (B1 -1-3) Component is preferably 0 to 20% by mass.

Further, when the polymerizable functional group to be introduced into the side chain of the photochromic polyrotaxane compound (A) is an OH group and/or an SH group, polyol (B3-1), polythiol (B3-2), polyamine (B3 -3), polyisocyanate (B3-4) and polyisothiacyanate (B3-5) so that a urethane bond, thiourethane bond, urea bond or thiourea bond (especially urethane bond or thiourethane bond) is formed Best used in combination.

In this case, the amount of SH groups and OH groups is 0.8 to 1.2 mol, in particular 0.85 to 1.15 mol, most preferably 0.9 to 1.1 mol, per mol of NCO group or NCS group. It should be in the molar range.

<Use of curable composition>
The curable composition of the present invention can use only the photochromic polyrotaxane compound (A) when a chain having a polymerizable group is introduced into the photochromic polyrotaxane compound (A). For example, a photochromic sheet (photochromic cured product) can be produced by sheet molding using the photochromic polyrotaxane compound (A).

Alternatively, the above-mentioned curable composition is dispersed or dissolved in an organic solvent to prepare a coating liquid, and this coating liquid is applied to a transparent optical sheet or optical film and dried to form a photochromic coating layer (photochromic curing layer). body), thereby expressing photochromic properties.

However, the curable composition of the present invention generally preferably contains a polymerizable compound (B) and a polymerization curing accelerator (C) in addition to the photochromic polyrotaxane compound (A). For example, it is desirable to melt-knead each component to prepare a photochromic composition, polymerize and cure the photochromic composition to prepare a photochromic cured body, and exhibit photochromic properties by the cured body. Hereinafter, an example in which a curable composition containing a polymerizable compound (B) is used as a photochromic cured product will be described. In the case of using only the photochromic polyrotaxane compound (A) into which a chain having a polymerizable group is introduced, Also, the same method as the method for curing the curable composition can be employed. Moreover, the photochromic polyrotaxane compound (A) contained in the curable composition may or may not have a polymerizable group.

Polymerization and curing for producing a photochromic cured product is carried out by irradiation with active energy rays such as ultraviolet rays, α rays, β rays, and γ rays, heat, or a combination of both to radical polymerization, ring-opening polymerization, anionic polymerization, or condensation. It is carried out by carrying out polymerization. That is, an appropriate polymerization means may be adopted according to the types of the polymerizable compound (B) and the polymerization curing accelerator (C) and the form of the photochromic cured body to be formed.

When thermally polymerizing the curable composition of the present invention containing the polymerizable compound (B), etc., the temperature particularly affects the properties of the resulting photochromic cured product. This temperature condition is affected by the type and amount of the thermal polymerization initiator and the type of the polymerizable compound, so it cannot be generally limited, but generally the polymerization starts at a relatively low temperature and the temperature is raised slowly. A method is preferred. As with temperature, the polymerization time also varies depending on various factors, so it is preferable to determine the optimum time according to these conditions in advance. preferred to choose. When obtaining a photochromic laminated sheet, it is preferable to carry out the polymerization at a temperature at which the reaction between the polymerizable functional groups proceeds, and to determine the optimum temperature and time so as to obtain the target molecular weight.

Further, when the curable composition of the present invention is photopolymerized, among the polymerization conditions, the UV intensity, in particular, affects the properties of the resulting photochromic cured product. This illuminance condition is affected by the type and amount of the ^{photopolymerization} initiator and the type of the polymerizable monomer, so it cannot be generally limited. It is preferable to select the conditions so that light irradiation is performed for 5 to 5 minutes.

When the photochromic property is expressed by the kneading method using the polymerization curing described above, the curable composition is injected between the glass molds held by the elastomer gasket or spacer, and the polymerizable compound ( Depending on the type of B) and polymerization curing accelerator, a photochromic cured body molded into the form of an optical material such as a lens is obtained by cast polymerization by heating in an air furnace or irradiation with active energy rays such as ultraviolet rays. be able to.

According to such a method, a spectacle lens or the like imparted with photochromic properties can be obtained directly.

When photochromic properties are exhibited by a lamination method, a coating liquid is prepared by dissolving the curable composition in an appropriate organic solvent, and the coating liquid is applied to the surface of an optical substrate such as a lens substrate by spin coating, dipping, or the like. is applied, dried to remove the organic solvent, and then polymerized and cured by UV irradiation or heating in an inert gas such as nitrogen to form a photochromic cured body on the surface of the optical substrate. is formed (coating method).

Alternatively, an optical substrate such as a lens base material is placed facing a glass mold so as to form a predetermined gap, a curable composition is injected into this gap, and in this state, polymerization is performed by UV irradiation, heating, or the like. A photochromic layer composed of a photochromic cured product can also be formed on the surface of an optical substrate by casting polymerization using an inner mold that performs curing (casting polymerization method).

When the photochromic layer is formed on the surface of the optical substrate by the lamination method (coating method and cast polymerization method) as described above, the surface of the optical substrate is chemically treated with an alkaline solution, an acid solution, or the like in advance. Adhesion between the photochromic layer and the optical substrate can be enhanced by performing physical treatment such as corona discharge, plasma discharge, and polishing. Of course, it is also possible to provide a transparent adhesive resin layer on the surface of the optical substrate.

Furthermore, when photochromic properties are exhibited by a binder method, a photochromic sheet is produced by sheet molding using a curable composition, and this is sandwiched between two transparent sheets (optical sheets), and the polymerization described above is performed. By curing, a photochromic laminate having the photochromic layer as an adhesive layer is obtained.

In this case, a means of coating using a coating liquid obtained by dissolving a curable composition in an organic solvent can also be employed to prepare the photochromic sheet.

The photochromic laminate thus produced is, for example, mounted in a mold, and then injection-molded with a thermoplastic resin (for example, polycarbonate) for optical substrates such as lenses to impart photochromic properties. This photochromic laminate can be adhered to the surface of the optical substrate with an adhesive or the like, thereby obtaining a photochromic lens. .

In the case of producing a photochromic laminate as described above, urethane or urea-based polymerizable compound (B3), particularly urethane-based Preferably, a polymerizable compound is used and adjusted to form a polyurethane.

The above-described curable composition of the present invention can express photochromic properties excellent in color density, color fading speed, etc., and is imparted with photochromic properties without reducing properties such as mechanical strength. It is effectively used for the production of optical substrates such as photochromic lenses.

In addition, the photochromic layer and photochromic cured product formed from the curable composition of the present invention can be dyed with dyes such as disperse dyes, silane coupling agents, silicon, zirconium, antimony, aluminum, tin, etc., depending on the application. , preparation of a hard coat film using a hard coat agent containing a sol such as tungsten as a main component, formation of a thin film by vapor deposition of a metal oxide such as SiO ₂ , TiO ₂ , ZrO ₂ , and application of an organic polymer It is also possible to perform post-processing such as antireflection treatment and antistatic treatment with a thin film.

EXAMPLES Next, the present invention will be described in detail using Examples and Comparative Examples, but the present invention is not limited to these Examples. First, the measuring apparatus used in the present invention, the manufacturing method of each component, and the like will be described.

(Molecular weight measurement; gel permeation chromatography (GPC measurement))
For GPC measurement, a liquid chromatograph (manufactured by Nippon Waters Co., Ltd.) was used as an apparatus. Depending on the molecular weight of the sample to be analyzed, the columns are Shodex GPC KF-802 (exclusion limit molecular weight: 5,000), KF802.5 (exclusion limit molecular weight: 20,000), KF-803 (exclusion limit molecular weight: 70,000), KF-804 (exclusion limit molecular weight: 400,000), and KF-805 (exclusion limit molecular weight: 2,000,000) were used as appropriate. In addition, dimethylformamide (DMF) was used as a developing solution, and the measurement was performed under conditions of a flow rate of 1 ml/min and a temperature of 40°C. Using polystyrene as a standard sample, the weight average molecular weight was determined by comparative conversion. A differential refractometer was used as a detector.

Example 1
Synthesis of a photochromic polyrotaxane compound (PR1) with a chain containing a photochromic moiety.

First step The following formula (11) synthesized according to the method described in International Publication No. 2005/028465 pamphlet

52.3 g (100 mmol) of the compound represented by the following formula (12)

To 44.8 g (150 mmol) of the compound represented by and 2.5 g (10 mmol) of pyridinium p-toluenesulfonate, 1 L of toluene was added, and the mixture was heated and stirred at 75° C. for 2 hours. After cooling to room temperature, the mixture was washed with 1 L of water three times, and the organic layer was distilled off under reduced pressure. The obtained residue is purified by silica gel column chromatography, and the following formula (13)

48.2 g of the compound represented by are obtained. Yield was 60%.

Second step To 48.2 g (60 mmol) of the compound represented by the above formula (13), 9.0 g (90 mmol) of succinic anhydride, and 18.6 g (90 mmol) of dicyclohexylcarbodiimide, 1 L of tetrahydrofuran (THF) was added, and Stirred for an hour. After filtering off the precipitate, THF was distilled off under reduced pressure, and the obtained residue was purified by silica gel chromatography, and the following formula (14)

37.9 g (42 mmol) of the compound represented by were obtained. Yield was 70%.

Third step According to the method described in International Publication No. 2013/099842, the chain portion of the axial molecule is formed of polyethylene glycol having a molecular weight of 11,000, the bulky groups at both ends are adamantyl groups, and the cyclic molecule is An α-cyclodextrin ring was synthesized by ring-opening polymerization of 3.5 molecules of ε-caprolactone on average via a propyloxy group (pr1; Reference Example 1). The properties of pr1 (Reference Example 1) are shown below.
Inclusion amount of α-cyclodextrin: 0.25.
Degree of modification of side chains: 0.5 (50%).
Side chain molecular weight (first side chain molecular weight): about 450 on average.
Weight average molecular weight Mw (GPC): 180,000.

500 mL of THF was added to 10.0 g of the above compound (pr1; Reference Example 1), 4.8 g (5.3 mmol) of the compound represented by the above formula (14), and 2.1 g (10 mmol) of dicyclohexylcarbodiimide, and the mixture was stirred at room temperature for 120 hours. . After confirming disappearance of the compound represented by the above formula (14) by HPLC (high performance liquid chromatography), the precipitate was filtered off. The obtained solution is dropped into hexane, and the precipitated solid is collected and dried to give the following formula (15)

Thus, 12 g of a photochromic polyrotaxane compound (PR1) having a side chain containing a photochromic site represented by was obtained.

The properties of the obtained photochromic polyrotaxane compound (PR1) are shown below.
Inclusion amount of α-cyclodextrin: 0.25.
Modification degree of side chain measured by 1H-NMR: 0.5 (50%).
Molecular weight of first side chain: about 450 on average.
Molecular weight of side chains containing photochromic moieties: average about 610 (excluding photochromic moieties).
Weight average molecular weight Mw (GPC): 270,000.

These results show that PR1 has a structure in which photochromic sites are introduced into 35% of the side chains and 65% of the side chains have terminal OH groups. The results of ¹ H-NMR measurements showed that chains with an average of about 100 photochromic sites were introduced per molecule.
Table 1 summarizes the properties of the obtained photochromic polyrotaxane compound (PR1).

Example 2
Synthesis of a photochromic polyrotaxane compound (PR2) having a chain containing a photochromic moiety and a chain containing an acryl group as a polymerizable group.

10.0 g of (PR1) synthesized in Example 1 was dissolved in 50 mL of methyl ethyl ketone, 5 mg of dibutylhydroxytoluene (polymerization inhibitor) was added, and then 0.73 g (5.1 mmol) of 2-acryloyloxyethyl isocyanate was added dropwise. did. 10 mg of dibutyltin dilaurate was added as a catalyst, and the mixture was heated and stirred at 70° C. for 4 hours. This solution is dropped into hexane, and the precipitated solid is collected and dried to obtain a chain containing a photochromic site represented by the above formula (15) and the following formula (16).

10 g of a photochromic polyrotaxane compound (PR2) having a chain containing an acrylic group as a polymerizable group was obtained.

The properties of the obtained photochromic polyrotaxane compound (PR2) are shown below.
Inclusion amount of α-cyclodextrin: 0.25.
Degree of modification of side chains: 0.5 (50%).
Molecular weight of first side chain: about 450 on average.
Molecular weight of the chain containing the photochromic portion: average about 610 (excluding the photochromic portion).
Molecular weight of chains containing polymerizable groups (acrylic groups): about 540 on average (excluding polymerizable groups).
Weight average molecular weight Mw (GPC): 290,000.

From this result, PR2 has a structure in which a photochromic site is introduced to 35% of the side chains, an acrylic group is introduced as a polymerizable group to 50% of the side chains, and 15% of the side chains have an OH group at the end. I know there is. Further, from the results of ¹ H-NMR measurement, a chain having an average of about 100 photochromic sites per molecule was introduced, and a chain having an average of about 140 polymerizable groups (acrylic groups) was introduced. I found out.
Table 1 shows the properties of the obtained photochromic polyrotaxane compound (PR2).

Example 3
Synthesis of a photochromic polyrotaxane compound (PR3) with a chain containing a photochromic moiety.

In Example 1, the same operation was performed except that 0.14 g (0.15 mmol) of the compound represented by the above formula (14) and 0.041 g (0.2 mmol) of dicyclohexylcarbodiimide were used. ) to obtain 9 g of a photochromic polyrotaxane compound (PR3) having a chain containing a photochromic site represented by ).

The properties of the obtained photochromic polyrotaxane compound (PR3) are shown below.
Inclusion amount of α-cyclodextrin: 0.25.
Degree of modification of side chains: 0.5 (50%).
Molecular weight of first side chain: about 450 on average.
Molecular weight of the chain containing the photochromic portion: average about 610 (excluding the photochromic portion).
Weight average molecular weight Mw (GPC): 180,000.

These results show that PR3 has a structure in which a photochromic site is introduced into 1% of the side chains and 99% of the side chains have terminal OH groups. ¹ H-NMR measurement results also revealed that a chain having an average of about 3 photochromic sites per molecule was introduced.
Table 1 shows the properties of the obtained photochromic polyrotaxane compound (PR3).

Example 4
Synthesis of a photochromic polyrotaxane compound (PR4) having a chain containing a photochromic moiety and a chain containing an epoxy group as a polymerizable group.

10.0 g of (PR3) synthesized in Example 3 was dissolved in 100 mL of tetrahydrofuran, and 0.97 g (10.4 mmol) of epichlorohydrin and sodium hydride (oil was removed by washing with tetrahydrofuran) were added to the pure content of 0. .72 g (30 mmol) was added, and the mixture was heated and stirred at 60° C. for 48 hours. After adding 100 mL of toluene, the mixture was washed with 100 mL of water three times. This solution is dropped into hexane, and the precipitated solid is collected and dried to obtain a side chain containing a photochromic site represented by the above formula (15) and the following formula (17).

to obtain 9 g of a photochromic polyrotaxane compound (PR4) having a side chain containing an epoxy group as a polymerizable group.

The properties of the obtained photochromic polyrotaxane compound (PR4) are shown below.
Inclusion amount of α-cyclodextrin: 0.25.
Degree of modification of side chains: 0.5 (50%).
Molecular weight of first side chain: about 450 on average.
Molecular weight of the chain containing the photochromic portion: average about 610 (excluding the photochromic portion).
Molecular weight of chains containing polymerizable groups (epoxy groups): about 460 on average (excluding polymerizable groups).
Weight average molecular weight Mw (GPC): 190,000.

From this result, PR4 has a structure in which a photochromic site is introduced into 1% of the side chains, an epoxy group is introduced as a polymerizable group into 70% of the side chains, and 29% of the side chains have an OH group at the end. I know there is. Further, from the ¹ H-NMR measurement results, a chain having an average of about 3 photochromic sites per molecule was introduced, and a chain having an average of about 190 polymerizable groups (epoxy groups) was introduced. I found out.
Table 1 shows the properties of the obtained photochromic polyrotaxane compound (PR4).

Example 5
Preparation of curable composition (Y1 (hereinafter sometimes simply referred to as (Y1))) and preparation and evaluation of photochromic cured body (Preparation of curable composition)
A photochromic curable composition (Y1) was prepared by thoroughly mixing each component according to the following recipe.

prescription;
(A) Photochromic polyrotaxane compound PR1 (manufactured in Example 1) 7 parts by mass.

(B) Polymerizable compound (B1-1-1-1) Component polyethylene glycol dimethacrylate (average molecular weight 736) 45 parts by mass.
(B1-1-1-1) Component polyethylene glycol dimethacrylate (average molecular weight: 536) 7 parts by mass.
(B1-1-2-1) component
40 parts by mass of trimethylolpropane trimethacrylate.
(B1-1-3) Component γ-methacryloyloxypropyltrimethoxysilane 2 parts by mass.
Glycidyl methacrylate 1 part by mass.

(C) Polymerization Curing Accelerator Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name: Irgacure 819, manufactured by BASF) (polymerization initiator) 0.3 parts by mass.

(Other compounding agents)
Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight 508) (stabilizer) 3 parts by mass.
Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (manufactured by Ciba Specialty Chemicals, Irganox245) (stabilizer) 3 parts by mass.
Dow Corning Toray Co., Ltd. trade name; L7001 (leveling agent) 0.1 part by mass.

When the total amount of the present curable composition is 100 parts by mass, the mass corresponding to the photochromic site is calculated to be about 2% by mass.

(Preparation and Evaluation of Photochromic Laminate (Photochromic Cured Body))
A photochromic laminate was obtained by a lamination method using the curable composition (Y1). The polymerization method is shown below.

First, a thiourethane plastic lens having a central thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. The thiourethane-based plastic lens was previously subjected to alkali etching using a 10% aqueous sodium hydroxide solution at 50° C. for 5 minutes, and then thoroughly washed with distilled water.

Using a spin coater (1H-DX2, manufactured by MIKASA), a moisture-curable primer (product name: TR-SC-P, manufactured by Tokuyama Co., Ltd.) is applied to the surface of the above plastic lens at a rotation speed of 70 rpm for 15 seconds. It was then coated at 1000 rpm for 10 seconds. After that, about 2 g of the photochromic composition obtained above was spin-coated at 60 rpm for 40 seconds and then at 600 rpm for 10 to 20 seconds so that the photochromic coating layer had a film thickness of 40 μm.

The lens coated with the coating agent on the surface was irradiated with light for 90 seconds using a metal halide lamp with an output of 200 mW/cm ² in a nitrogen gas atmosphere to cure the coating film. After that, it was further heated at 110° C. for 1 hour to produce a photochromic laminate having a photochromic layer.

The resulting photochromic laminate was used as a sample, and a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. was passed through an aeromass filter (manufactured by Corning) at 20 ± 1 ° C., and the polymer (Photochromic coat layer) The surface was irradiated with a beam intensity of 365 nm = 2.4 mW/cm ² and 245 nm = 24 µW/cm ² for 120 seconds to develop color, and the photochromic properties of the photochromic layered product were measured. Each photochromic property and film properties such as Vickers hardness were evaluated by the following methods, and are shown in Table 2.

・Maximum absorption wavelength (λmax):
It is the maximum absorption wavelength after color development determined by a spectrophotometer (instantaneous multichannel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone during color development.

・ Color density {ε (120) - ε (0)}:
The difference between the absorbance {ε(120)} after light irradiation for 120 seconds and the absorbance ε(0) before light irradiation at the maximum absorption wavelength. It can be said that the higher the value, the better the photochromic properties.

- Fading speed [t1/2 (sec.)]:
Time required for the absorbance at the maximum absorption wavelength of the sample to decrease to 1/2 of {ε(120)−ε(0)} after light irradiation for 120 seconds. It can be said that the shorter the time, the better the photochromic properties.

- Vickers hardness Vickers hardness was measured using a hardness meter with an automatic measuring (reading) device (PMT-X7A, manufactured by Matsuzawa Co., Ltd.). Specifically, a Vickers indenter of 10 gf was pressed into the surface of the sample for 30 seconds, and the Vickers hardness was obtained from the indentation. Vickers hardness is an indicator of whether or not the lens will be scratched during the lens processing process. As a guideline, if the Vickers hardness exceeds 4.5, scratches are difficult to occur, and if it is 4.5 or less, scratches are likely to occur.

- Cloudiness The molded photochromic laminate was visually evaluated for cloudiness under direct Nicols.
1: At a level that does not pose a problem as a product, there is no cloudiness, or it is hardly visible.
2: The product is at a level that does not pose a problem, but is slightly cloudy.
3: The level is satisfactory as a product, but the cloudiness is stronger than that of 2.
4: There is cloudiness and cannot be used as a product.
・Moldability:
The optical distortion of the molded photochromic laminate was visually observed. Evaluation was made according to the following criteria.
1: No optical distortion.
2: Optical distortion is observed in a part of half or less of the lens.
3: Optical distortion is observed over the entire lens.

Example 6
Preparation of curable composition (Y2 (hereinafter sometimes simply referred to as (Y2))) Instead of 7 parts by mass of the photochromic polyrotaxane compound (PR1) obtained in Example 1, the photochromic property obtained in Example 2 A photochromic curable composition (Y2) was prepared in the same manner as in Example 5, except that 7 parts by mass of the polyrotaxane compound (PR2; produced in Example 2) was used.

When the total amount of the present curable composition is 100 parts by mass, the mass corresponding to the photochromic site is calculated to be about 2% by mass.

(Preparation and Evaluation of Photochromic Laminate)
A photochromic laminate was obtained by the lamination method in the same manner as in Example 5, except that the curable composition (Y2) was used, and evaluated. Table 2 shows the results.

Example 7
Preparation of curable composition (Y3 (hereinafter sometimes simply referred to as (Y3)))
A curable composition was prepared by mixing each component according to the following recipe. Each compounding amount is shown below.

prescription;
(A) Photochromic polyrotaxane compound PR3 (manufactured in Example 3) 3 parts by mass.

(B) a polymerizable compound
(B3-2) Component DPMP: Dipentaerythritol hexakis (3-mercaptopropionate) 38 parts by mass.
EGMP-4: 21 parts by mass of tetraethylene glycol bis(3-mercaptopropionate).
(B3-4) Component XDI: m-xylene diisocyanate 38 parts by mass.

(C) Polymerization curing accelerator DBTD: 0.1 part by mass of dibutyltin dilaurate (catalyst).

(Other compounding agents)
DBP: Di-n-butyltin (release agent) 0.3 parts by mass.

When the total amount of the curable composition is 100 parts by mass, the mass corresponding to the photochromic site is calculated to be about 0.04% by mass.

A photochromic cured body was obtained by a kneading method using the above curable composition. The polymerization method is shown below.

That is, after the curable composition is sufficiently defoamed, it is poured into a mold having a thickness of 2 mm, which is composed of a glass mold subjected to mold release treatment and a gasket made of ethylene-vinyl acetate copolymer. modeled.

Then, while gradually raising the temperature from 30° C. to 95° C., it was cured over 15 hours. After the polymerization was completed, the photochromic cured body was removed from the glass of the mold. The maximum absorption wavelength, color density, color fading speed, cloudiness, and moldability of the obtained photochromic cured product were evaluated in the same manner as in Example 5. Moreover, the evaluation of the L scale Rockwell hardness was performed as follows.

L scale Rockwell hardness (HL):
After holding the cured product in a room at 25° C. for one day, the L-scale Rockwell hardness of the photochromic cured product was measured using an Akashi Rockwell hardness tester (type: AR-10). Table 2 shows the results.

Example 8
Preparation of Curable Composition (Y4 (hereinafter sometimes simply referred to as (Y4))) A curable composition was prepared by mixing each component according to the following recipe. Each compounding amount is shown below.

prescription;
(A) Photochromic polyrotaxane compound PR4 (manufactured in Example 4) 3 parts by mass.

(B) Polymerizable compound (B2) Component neopentyl glycol diglycidyl ether 74 parts by mass.
Trimethylolpropane triglydisyl ether 23 parts by mass.

(C) Polymerization curing accelerator:
(C2-1) Component 1,8-diaza-bicyclo(5,4,0)-7-undecene (initiator) 3 parts by weight.

When the total amount of the curable composition is 100 parts by mass, the mass corresponding to the photochromic site is calculated to be about 0.08% by mass.

A photochromic cured body was obtained by a kneading method using the above curable composition. The polymerization method is shown below.

That is, after the curable composition is sufficiently defoamed, it is poured into a mold having a thickness of 2 mm, which is composed of a glass mold subjected to mold release treatment and a gasket made of ethylene-vinyl acetate copolymer. modeled.

Then, while gradually raising the temperature from 30° C. to 110° C., it was cured over 15 hours. After the polymerization was completed, the photochromic cured body was removed from the glass of the mold.

The maximum absorption wavelength, color density, fading rate, opacity, moldability, and L-scale Rockwell hardness were evaluated in the same manner as in Example 7. Table 2 shows the results.

Reference example 2
Synthesis of a polyrotaxane compound having a chain containing a polymerizable group and not having a chain containing a photochromic site )) was dissolved in 50 mL of methyl ethyl ketone, 5 mg of dibutylhydroxytoluene (polymerization inhibitor) was added, and then 1.07 g (7.6 mmol) of 2-acryloyloxyethyl isocyanate was added dropwise. 10 mg of dibutyltin dilaurate was added as a catalyst, and the mixture was heated and stirred at 70° C. for 4 hours. This solution was dropped into hexane, and the precipitated solid was collected and dried to obtain 10 g of a polyrotaxane compound (pr2) having a chain containing an acrylic group as a polymerizable group represented by the above formula (16). .

The properties of the obtained polyrotaxane compound (pr2) are shown below.
Inclusion amount of α-cyclodextrin: 0.25.
Degree of modification of side chains: 0.5 (50%).
Side chain molecular weight (first side chain molecular weight): about 100 on average.
Molecular weight of chains containing polymerizable groups (acrylic groups): about 650 on average (excluding polymerizable groups).
Weight average molecular weight Mw (GPC): 200,000

These results show that pr2 has a structure in which acrylic groups are introduced as polymerizable groups into 50% of the side chains, and 50% of the side chains have OH groups at their terminals. Further, from the results of ¹ H-NMR measurement, it was found that a chain having an average of about 140 polymerizable groups (acrylic groups) per molecule was introduced.
Table 1 shows the properties of the obtained polyrotaxane compound (pr2). In addition, the properties of the compound (pr1; Reference Example 1) produced in the third step of Example 1 are also shown in Table 1.

Comparative example 1
Preparation of curable composition (y1 (hereinafter sometimes simply referred to as (y1))) Instead of 7 parts by mass of the photochromic polyrotaxane compound (PR1) obtained in Example 1, the polymerizable polymer obtained in Reference Example 2 5 parts by mass of a polyrotaxane compound (pr2) having a chain containing an acrylic group as a group,
Furthermore, as another compounding agent, the following formula (18)

A curable composition (y1) was prepared in the same manner as in Example 5 except that 2 parts by mass of the photochromic compound represented by was used.

(Preparation and Evaluation of Photochromic Laminate)
A photochromic laminate was obtained by the lamination method in the same manner as in Example 5 except that the curable composition (y1) was used, and evaluated. Table 2 shows the results.

Comparative example 2
Preparation of curable composition (y2 (hereinafter sometimes simply referred to as (y2))) Instead of 6 parts by mass of the photochromic polyrotaxane compound (PR3) obtained in Example 3, the polyrotaxane compound (pr1 (Reference Example 1 ), the compound produced in the third step of Example 1) was used in 3 parts by mass, and as another compounding agent, 0.04 parts by mass of the photochromic compound represented by the formula (18) was used in Example 7. A photochromic curable composition ( y2 ) was prepared in the same manner as above.

(Preparation and evaluation of photochromic cured body)
A photochromic cured product was obtained by a kneading method in the same manner as in Example 7 except that the curable composition (y2) was used, and was evaluated. Table 2 shows the results.

As is clear from the above examples and comparative examples, the photochromic laminate or the photochromic cured body obtained by polymerizing the curable composition of the present invention can arrange the photochromic site in the vicinity of the polyrotaxane compound. It is clear that it has the characteristics of high color development density and fast color fading speed.

Example 9 Synthesis of a photochromic polyrotaxane compound (PR5) with a chain containing a photochromic moiety.
Synthesis of polyrotaxane compound Production example First step Formula (19) below

4.7 g (10 mmol) of the compound represented by the following formula (20) synthesized according to the method described in WO 2006/022825 pamphlet

To 5.3 g (15 mmol) of the compound represented by and 0.25 (1 mmol) of pyridinium p-toluenesulfonate, 100 mL of toluene was added, and the mixture was heated and stirred at 75° C. for 1 hour. After cooling to room temperature, the mixture was washed with 100 mL of water three times, and the organic layer was distilled off under reduced pressure. The obtained residue is purified by silica gel column chromatography, and the following formula (21)

6.2 g of the compound represented by are obtained. Yield was 77%.

Second step To 6.2 g (7.7 mmol) of the compound represented by the above formula (21), 1.55 g (15.5 mmol) of succinic anhydride, and 1.95 g (19.3 mmol) of triethylamine, add 200 mL of dichloromethane, and stirred for 12 hours. After ice-cooling, 10% hydrochloric acid was slowly added until the pH reached 1, and liquid separation was performed. After washing with 250 mL of water three times, the organic layer was distilled off under reduced pressure. The resulting residue is purified by silica gel chromatography and represented by the following formula (22)

6.6 g (7.3 mmol) of the compound represented by were obtained. Yield was 95%.

Third step According to the method described in International Publication No. 2013/099842 pamphlet, the chain portion of the axial molecule is formed of polyethylene glycol having a molecular weight of 2,000, the bulky groups at both ends are adamantyl groups, and the cyclic molecule is An α-cyclodextrin ring in which an average of 8.5 propyloxy groups were introduced per molecule of α-cyclodextrin (pr3; Reference Example 3) was synthesized. The properties of pr3 (Reference Example 3) are shown below.
Inclusion amount of α-cyclodextrin: 50.
Degree of side chain modification: 0.47 (47%).
Weight average molecular weight Mw (GPC): 19,000.
10 mL of THF was added to 455 mg of the above compound (pr3; Reference Example 3), 280 mg (0.29 mmol) of the compound represented by the above formula (22), and 56 mg of dicyclohexylcarbodiimide, and the mixture was stirred at room temperature for 25 hours. After confirming disappearance of the compound represented by the above formula (22) by TLC (thin layer chromatography), the precipitate was filtered off. The obtained solution is dropped into methanol, and the precipitated solid is collected and dried to give the following formula (23)

Thus, 488 mg of a photochromic polyrotaxane compound having a side chain containing a photochromic site represented by was obtained.
Subsequently, 300 mg of the photochromic polyrotaxane compound represented by the formula (23) obtained above, 77 mg of succinic anhydride, and 0.11 ml of triethylamine were dissolved in 5.0 ml of dichloromethane and stirred at room temperature for 14 hours, followed by polyethylene glycol monomethyl ether. (Mw.550) 200 mg and dicyclohexylcarbodiimide 70 mg were added and stirred at room temperature for 18 hours. After filtering off the precipitate, the reaction solution was added to 50 ml of methanol to precipitate a solid. The precipitate is collected by centrifugation, and the obtained solid is further washed with methanol and then dried to give the following formula (24)

141 mg of a photochromic polyrotaxane compound (PR5) into which a polyethylene glycol monomethyl ether chain (first side chain (side chain)) was introduced was obtained.
The properties of the obtained photochromic polyrotaxane compound (PR5) are shown below.
Inclusion amount of α-cyclodextrin: 50.
Degree of side chain modification: 0.47 (47%).
Molecular weight of the first side chain: about 650 on average
Molecular weight of side chains containing photochromic moieties: average about 160 (excluding photochromic moieties).
Weight average molecular weight Mw (GPC): 76,000.
These results show that PR5 has a structure in which a photochromic site is introduced into 35% of the side chains and polyethylene glycol monomethyl ether (first side chain) is introduced into 35% of the side chains. ¹ H-NMR measurement results also revealed that a chain having an average of about 33 photochromic sites per molecule was introduced.
Table 3 summarizes the properties of the obtained photochromic polyrotaxane compound (PR5).

Example 10
Preparation of curable composition (Y5 (hereinafter sometimes simply referred to as (Y5))) and preparation and evaluation of photochromic cured body (Preparation of curable composition)
A photochromic curable composition (Y5) was prepared by thoroughly mixing each component according to the following recipe.
prescription;
(A) Photochromic polyrotaxane compound PR5 (manufactured in Example 9) 10.9 mg.
(B) Polymerizable compound (B1-1-3) methyl methacrylate: 5.5 g.
(B4-4) Hydroxypropyl methacrylate: 4.5 g.
(C) Polymerization curing accelerator azobisisobutyronitrile (polymerization initiator) 3.0 mg.

(Preparation and evaluation of photochromic cured body)
A photochromic cured body was obtained by a kneading method using the above curable composition (Y5). The polymerization method is shown below.
After the above-mentioned curable composition (Y5) was sufficiently defoamed, a mold consisting of a mold having a thickness of 2 mm and consisting of a glass mold subjected to mold release treatment and a gasket made of ethylene-vinyl acetate copolymer was used. cast. Then, while gradually raising the temperature from 30° C. to 95° C., it was cured over 15 hours. After the polymerization was completed, the photochromic cured body was removed from the glass of the mold.
The resulting photochromic cured product was evaluated in the same manner as in Example 7 (however, the L scale Rockwell hardness was not measured). Table 4 shows the results.

Comparative example 3
In Example 10, instead of (A) the photochromic polyrotaxane compound, the following formula (25)

The same operation and evaluation as in Example 10 were performed except that 4.0 mg of the photochromic compound represented by was used and the amount of the photochromic portion was the same as in Example 10. Table 4 shows the results.

Example 11
Preparation of curable composition (Y6 (hereinafter sometimes simply referred to as (Y6))) and preparation and evaluation of photochromic cured body (Preparation of curable composition)
A photochromic curable composition (Y6) was prepared by thoroughly mixing each component according to the following recipe.
prescription;
(A) Photochromic polyrotaxane compound PR5 (manufactured in Example 9) 10.9 mg.
(B) Polymerizable compound (B1-1-1-4) norbornene methane diisocyanate: 4.58 g.
(B3-2) Pentaerythritol tetrakis(3-mercaptopropionate): 5.42 g.
(C) Polymerization curing accelerator (C3-1) dimethyltin dichloride 10 mg.

(Preparation and evaluation of photochromic cured body)
Using the curable composition (Y6), a photochromic cured product was obtained by a kneading method. The polymerization method is shown below.
After the above-mentioned curable composition (Y6) was sufficiently defoamed, a mold consisting of a mold with a thickness of 2 mm, which was composed of a glass mold subjected to mold release treatment and a gasket made of ethylene-vinyl acetate copolymer, was used. cast. Then, while gradually raising the temperature from 30° C. to 95° C., it was cured over 15 hours. After the polymerization was completed, the photochromic cured body was removed from the glass of the mold.
The obtained photochromic cured product was evaluated in the same manner as in Example 10. Table 4 shows the results.

Comparative example 4
Example 11 except that 4.0 mg of the photochromic compound used in Comparative Example 3 was used in place of (A) the photochromic polyrotaxane compound in Example 11, and the amount of the photochromic portion was the same as in Example 11. The same operation was performed and the same evaluation was performed. Table 4 shows the results.

Claims (17)

A polyrotaxane compound comprising an axial molecule and a plurality of cyclic molecules surrounding the axial molecule, wherein at least one of the cyclic molecules is bound to a side chain containing a photochromic site ,
the cyclic molecule is a cyclodextrin ring
A photochromic polyrotaxane compound characterized by: 2. The photochromic polyrotaxane compound according to claim 1, further comprising a side chain containing a polymerizable group bound to at least one of said cyclic molecules. 2. The photochromic polyrotaxane compound according to claim 1, wherein the side chain containing the photochromic moiety has at least an ether bond. 4. The photochromic polyrotaxane compound according to claim 2 or 3, wherein the side chain containing the polymerizable group has at least an ether bond. 5. The axial molecule comprises a chain main chain and bulky groups at both ends thereof, the chain main chain being formed of polyethylene glycol, and the bulky groups at both ends being an adamantyl group. 2. The photochromic polyrotaxane compound according to item 1. 6. The photochromic polyrotaxane compound according to any one of claims 1 to 5 , wherein the photochromic moiety has at least one structure selected from the group consisting of naphthopyran, spirooxazine, spiropyran, fulgide, fulgimide and diarylethene. 7. The photochromic polyrotaxane compound according to claim 1, wherein the photochromic moiety is indeno[2,1-f]naphtho[1,2 - b]pyran. wherein the polymerizable group is selected from acrylic, methacrylic, allyl, vinyl, 4-vinylphenyl, epoxy, episulfide, thietanyl, OH, SH, _NH2 , NCO, and NCS groups; The photochromic polyrotaxane compound according to any one of claims 2 to 7 , which is at least one group selected from the group consisting of: The side chain containing the photochromic site is represented by the following formula (1)

here,
PC is a photochromic group,
R ¹ is a linear or branched alkylene group having 2 to 8 carbon atoms,
R ² is a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms having an acetyl group branch, or a carbon number having an ether bond is a linear or branched alkylene group of 3 to 8,
L is the following formula (2)

here,
R ³ is a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms;
R ⁴ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or 1 to 20 carbon atoms. is a dialkylsilyl group having a linear or branched alkyl group of
R ⁵ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms;
X ¹ and X ² are each independently a single bond, O, or NH;
c is an integer of 0 to 50, d is an integer of 0 to 50, e is an integer of 0 or 1,
when c is 2 or more, the parenthesized divalent groups of c may be the same or different,
When d is 2 or more, the parenthesized divalent groups of d may be the same or different,
is a divalent group represented by
a is an integer from 1 to 50, b is an integer from 0 to 50,
when a is 2 or more, the parenthesized divalent groups of a may be the same or different,
When b is 2 or more, the parenthesized divalent groups of b may be the same or different,
The photochromic polyrotaxane compound according to any one of claims 1 to 8 , wherein The side chain containing the polymerizable group is represented by the following formula (3)

here,
Z is a polymerizable group,
R ⁶ is a linear or branched alkylene group having 2 to 8 carbon atoms,
R ⁷ is a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms having an acetyl group branch, or a carbon number having an ether bond is a linear or branched alkylene group of 3 to 8,
L' is the following formula (2')

here,
R ³¹ is a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms,
R ⁴¹ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or 1 to 20 carbon atoms. is a dialkylsilyl group having a linear or branched alkyl group of
R ⁵¹ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms;
X ¹¹ and X ²¹ are each independently a single bond, O, or NH;
c ₁ is an integer of 0 to 50, d ₁ is an integer of 0 to 50, e ₁ is an integer of 0 or 1,
When c ₁ is 2 or more, the divalent groups may be the same or different,
When d ₁ is 2 or more, the divalent groups may be the same or different.
is a divalent group represented by
f is an integer from 1 to 50, g is an integer from 0 to 50,
When f is 2 or more, the divalent groups may be the same or different,
When g is 2 or more, the divalent groups may be the same or different,
The photochromic polyrotaxane compound according to any one of claims 2 to 9 , which is 1 to 100% of the side chains bonded to the cyclodextrin ring are side chains containing the photochromic site, and 0 to 99% are side chains having the polymerizable group. 10. The photochromic polyrotaxane compound according to any one of 9 . A curable composition comprising the photochromic polyrotaxane compound according to any one of claims 1 to 11 and a polymerizable compound other than the photochromic polyrotaxane compound. The polymerizable compound other than the photochromic polyrotaxane compound is a compound having at least one radically polymerizable group selected from the group consisting of an acrylic group, a methacrylic group, an allyl group, a vinyl group, and a 4-vinylphenyl group. 13. The curable composition of claim 12 . 13. The curable composition according to claim 12 , wherein the polymerizable compound other than the photochromic polyrotaxane compound is a compound having at least one polymerizable group selected from the group consisting of epoxy group, episulfide group and thietanyl group. thing. The polymerizable compound other than the photochromic polyrotaxane compound is a compound having at least one polymerizable group selected from the group consisting of OH group, SH group, _NH2 group, NCO group and NCS group. 13. The curable composition according to 12 . A photochromic cured product obtained by curing the photochromic polyrotaxane compound according to any one of claims 2 to 11 . A photochromic cured body obtained by curing the curable composition according to any one of claims 12 to 15 .

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